SPE 77472

Pollut-Eval: an innovative tool for direct hydrocarbon characterization

in oil base mud & cuttings
Yves Benoit, IFP/ Christine Dalmazzone, IFP-SPE / Annie Audibert-Hayet, IFP-SPE.
Copyright 2002, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the SPE Annual Technical Conference and
Exhibition held in San Antonio, Texas, 29 September2 October 2002.
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Abstract
Throughout the world, the drilling process generates a huge
variety of contaminated solid waste. The environmental
impact of these side products depends on their composition
and concentration but also on the employed drilling
technologies, based on water base mud (WBM) or oil base
mud (OBM).
The various local and international Guidelines will gradually
ban the discharge into the sea of these contaminated
drilling waste.
The OSPAR 2000/3 decisions will soon prohibit their
disposal into the sea and will recommend a zero %
discharge of organic based drilling fluids.
With the emphasis placed on environmental safety, the oil
companies are developing economical methodologies to
clean oil contaminated field waste, such as cuttings or used
drilling muds. One of the major challenge is to develop
sensitive analytical tool to measure in a short time low oil
content in a great variety of mineral matrix without major
interference.
In this framework, this paper provides answers
concerning the problem of quantification of low oil content in
complex solid waste. A study has been performed to
demonstrate the ability of the Pollut-Eval method to
characterize and quantify hydrocarbon contamination without
any pretreatment. In a first step, analytical results of pure
hydrocarbon cuts commonly used in drilling muds (iso and nparaffin, olefin, ester and diesel cuts) will be presented to
demonstrate the qualitative and quantitative efficiency of the
method.

In a second step, evaluation of the total organic content of

various drilling muds will be compared to their hydrocarbon
concentration to demonstrate that no major interference
occurred in the characterization or quantification of these
petroleum cuts despite the various and complex mud
formulations. In a last step, Pollut-Eval residual oil content
(ROC) and total organic carbon (TOC) of undersea
discharged cuttings sampled at 200 m depth (more or less
distant from an offshore rig) will be presented and compared
to capillary gas phase chromatography results.
As a conclusion, Pollut-eval performance will be
discussed and compared to other methods commonly used in
oil industry: global carbon organic determination by catalytic
oxidation and retort kit distillation.
Introduction
For a few years, the recent international recommendations
and Guidelines concerning the final disposal of drilling fluids
have obliged the drilling industry to serious control of waste
release.
To be efficient, the monitoring methodologies should be
applied to all drilling formulations whatever their
hydrocarbon or organic composition. At the end of the
drilling process, the efficiency of the solid waste posttreatment should also be taken into account.
Because the drilling activities are producing huge amount
of contaminated waste in the form of cuttings (2%) or
hydrocarbon based drilling mud (89%), oil companies are
seeking economical methodologies to clean up solid waste
produced as by-products. Whatever the technology chosen in
clean up operations, the need of an accurate monitoring is
stringent and should be included in the global cost evaluation
of the process (gravel to grave concept).
As a zero % discharge becomes more and more evident,
2 main technological options will be available in the next
years before the final disposal of the drilling waste:
- ship to shore for further treatments such as
bioremdiation, incineration, solvent washing or
thermic desorption.
- cuttings rinjection techniques

YVES BENOIT

Whatever the post-treatment, prevention of the risks should

be included very early in the development phase and
provided by adequate analytical tools.
In order to prevent the risk of hydrocarbon propagation in
geological formations, the cuttings reinjection techniques will
impose a precise knowledge of residual oil content
before discharge.
The development of more ecological post-treatment
process will impose an accurate hydrocarbon monitoring
performed by sensitive techniques able to differentiate
organic matter from hydrocarbon pollutants. The
development of such analytical tools would represent new
service dedicated to offshore and on shore oil industry.
Analytical methods and materials
1.

SPE 77472

carbon (TOC) of the sample. If the organic matrix releases

some hydrocarbons, they are separately quantified. Thus, the
Pollut-Eval provides a complete carbon mass balance in a
short duration. This method, based on the Rock-Eval
methodology, has already proved his efficiency to evaluate
low residual oil content (ref1).
In a second step, IFP has developed a Field PollutEval analyser which is transportable and dedicated to on-site
diagnosis. The analyser can be implemented at all stages
from initial diagnosis to the checking of the site treatment
efficiency. Furthermore, if used on site, this analyser allows
to optimise the sampling operations. The Pollut-Eval is
therefore a complementary analysis technique to commonly
laboratory used methodologies (CPG, IR).
Principle of the analysis

Pollut-Eval methods

Introduction
The Pollut-Eval method is based on the Rock-Eval
method, developed by IFP in the eighties for oil exploration
requirements [Espitali et al., 1986]. This method has proved
its capacity to detect and quantify hydrocarbon present in
rock samples. So, IFP decided, in the framework of the
EUREKA-RESCOPP European project, to extend this
methodology to the field of environment. In a first step, a
new device has therefore been developed, the Laboratory
Pollut-Eval analyser, dedicated to oil-contaminated soils
analysis [Ducreux et al., 1997].
The Pollut-Eval allows saving much time by carrying
out the analysis directly on the polluted soil sample without
extraction. This analyser provides, in a single analysis, the
type and quantity of hydrocarbons and the total organic

For the laboratory analyser, optional equipment are

available. The description presented below is the most
complete version.
For the field analyser, the equipment is limited to the
pyrolysis oven with a cooled autosampler.
The Laboratory Pollut-Eval method includes two
successive steps, a first heating in the pyrolysis oven, then a
second heating in the oxidation oven. An automaton is in
charge of the successive phases into both ovens.
In the pyrolysis oven swept by an inert gas (Nitrogen),
the soil sample is heated according to a temperature program
from 80C to 650C. In this way we obtain the
thermovaporisation of hydrocarbons and over 350 C, the
pyrolysis of heavy hydrocarbons (cracking). The analysis
cycle has been adjusted to various oil fractions (crude oil,
gasoline, heavy oils, lubricants, etc...).
Hydrocarbons are quantified by a flame ionisation
detector (FID), and at the same time an infra-red cell (IR)
continuously measures the CO and CO2 releases due to the
degradation of organic matter.
Then, in the oxidation oven swept by air, the sample is
heated according to a temperature program from 350 C to
850 C. The releases of CO and CO2 are always measured by
infra-red (IR). We can then observe the combustion of
residual organic carbon (RC) and, after this, the
decomposition of carbonates if any in the sample.
Analysis procedure
The sample is at first weighted in a small metallic
crucible; the amount of sample to analyse is between 100 and

SPE 77472

POLLUT-EVAL: A NOVEL TOOL FOR DIRECT HYDROCARBON ANALYSIS IN CONTAMINATED SOILS

300 mg. The Rocksix software, installed on the control and

acquisition workstation, allows to record all information
concerning the sample and to select the analysis cycle
(pyrolysis and/or oxidation), the detectors (FID and/or IR),
the temperature programme as well as the analysis order on
the carrousel.
Before the beginning of an analysis, the Pollut-Eval do
automatically the base line of the FID detector and purge the
infra-red cells. After this, the automaton puts the crucible into
the pyrolysis oven. As soon as the oven is closed the analysis
begins and then the following steps undergo :
First step of the analysis
- Isothermal and programmed thermovaporisation.
The sample is kept one minute at initial temperature
(80 C), which is then increased up to 120C at
25C/min.. The first cursor is placed at 90 C, the
peak obtained in this first integration area is labelled
"Q0" and the peak obtained between 90 and 120C is
labelled "Q1". The oven temperature is then raised to
350C at 25C/min.. The peaks obtained between 90
and 120C are labelled "Q2". In presence of organic
matter the CO and CO2 releases begin to appear,
resulting from thermal degradation of natural
organic matter.
- Programmed pyrolysis. The oven temperature is
raised from 350 to 650 C at 25 C/min. The hydrocarbons
with more than 40 carbon atoms are then cracked; the peak
obtained is labelled "Q3". The cracking of the organic matrix
may release some hydrocarbons but this quantity of
hydrocarbons is directly proportional to the quantity of CO
and CO2 released at the same time. This correlation allows
the quantification of heavy hydrocarbons even in presence of
a large quantity of organic matter.
The sum of the carbon quantities contained in the
hydrocarbons, in the CO and in the CO2 is called pyrolysable
carbon (PC).
Second step of the analysis
- Programmed oxidation. The initial temperature is
350 C, the sample is heated up to 850 C at 25 C/min. and
kept 3 minutes at this temperature. The releases of CO and
CO2 are always measured by infra-red. Between 350 and
650C we obtain one or two peaks corresponding to the
residual carbon (RC), these peaks are respectively labelled
"Q0" and "Q1". Over 650 C, we may observe an important
release of CO2 in presence of carbonates, this peak is labelled
"Q2".
The total organic carbon (TOC) is then obtained by
the sum of the pyrolysable carbon and the residual carbon
(TOC = PC + RC).
Characterisation and identification of hydrocarbons
In the pyrogram, we can note that each integration
area corresponds to a specific kind of hydrocarbons.
Comparisons of gas chromatography analysis and Pollut-Eval
analysis of the same sample allowed the determination of the
hydrocarbon range corresponding to each integration area.
These results showed that the Q0/Q1 areas limit corresponds
to C9-C10 hydrocarbons and the Q1/Q2 areas limit corresponds
to C12-C13 hydrocarbons. Concerning the limit between Q2

and Q3 areas, it is more difficult to determine precisely the

correspondence, the limit is about C40 hydrocarbons(ref2).
The tests executed at IFP in different conditions on
about twenty petroleum distillates have showed that the
proportions between the different integration areas are
characteristic of the pollutant type. Thus, to identify the
pollutant hydrocarbons, we use the relative value (identified
by the letter R and numbered from 0 to 3) of each integration
area : Rn = Qn / Q total x 100.
You can find below the characteristic values measured
on a sandy soil.
- Gasoline : R0 = 93%
- Diesel-oil : R2 = 74%
- Kerosene : R1 = 81%
- Sewage-oil : R3 = 75%
Quantification of the hydrocarbons
The quantification is executed in a classic way
through FID detector. However, some soils containing high
level of organic material release some hydrocarbons in
addition to CO and CO2. These hydrocarbons are detected by
the FID as well as the pollutant, and can therefore generate an
overestimation of the pollution level. This peak is distributed
as followed : 20% in Q2 area and 80% in Q3 area.
A study was carried out at IFP on soil samples
representative of the different organic matrixes that the
Pollut-Eval will have to encounter (ref2). This study allowed
the determination of the existing relations between infra-red
and FID signals, in order to calculate the proportion of the
FID signal due to indigenous organic material.
The equations established are used to calculate the
hydrocarbon quantity released by the cracking of the organic
matrix. The calculated quantity is distributed on the two
concerned areas and the obtained values are deduced from the
measures. Therefore, this method allows quantification of
hydrocarbons with more than 40 carbon atoms whatever the
type of soil.
Most important parameters
There are 4 integration areas in the pyrolysis step (n
from 0 to 3) and 3 in the oxidation step (n from 0 to 2).
The most important parameters are :
- the measured quantities
(Qn in pyrolysis and Qn in oxidation),
- the relative values for the FID signal (Rn),
- the total measured quantities
(Qt in pyrolysis and Qt in oxidation),
- the quantity of hydrocarbons released by the
cracking of the organic matrix (MO) and the
corrected values (QnC, RnC and QtC)
Furthermore, as in the Rock-Eval method, we use :
- the pyrolysable carbon (PC),
- the residual carbon (RC),
- the mineral carbon (MINC),
- the total organic carbon (TOC).
Screening of contaminated sites

YVES BENOIT

The Pollut-Eval offers the advantage of being

specially adapted to the analysis of a great number of samples
in order to establish a fast mapping of the pollution extension
on the studied site. In fact, the Rockint software can present
the
contamination level content as a function of the sampling
depth.
By this way, a two-dimensional contamination profile
of underground samples (corresponding to each sampling
point) is available (ref2). Then, by placing the obtained
profile side by side, the determination the three-dimensional
distribution of the pollutants is provided. Each profile can
optimise the sampling campaign and avoid useless
core sampling.
2.

To demonstrate the qualitative and quantitative efficiency of

the method for the concerned operators, most of the
hydrocarbon chosen are commercially available: n paraffin
more or less aromatic, olefin, diesel oil and ester included
in low tox formulations. A single rate cycle of 25C/min has
been applied to precisely known amount of pure compounds
introduced in the crucible of the analyzer between 2 layers of
clean heated sand. As shown in the table 2, the loss of the
most volatile fraction before the start of the analysis leads to
an under estimation of the theoretical concentration of these
pure hydrocarbons (expected to 100%).
The results presented below are the average values of
3 determinations.
reference

Theoretical
concentration

Ref 1
Ref 2
Ref 3
Ref 4
Ref 5
Ref 6
Ref 7
Ref 8

100%
100%
100%
100%
100%
100%
100%
100%

Retort Kit method

This methodology has been commonly used for 20 years in

the oil industry especially for the determination of the
water/oil/solid ratio in drilling fluids. Its principle is based on
the distillation of the two-phase oil/water mixture at 500C.
After condensation of the extracted vapor, a visual reading of
the water/oil content is provided. As many visual
determination, the manual evaluation leads to large variations
and uncertainty. Different types of analytical cells and test
tubes are adapted to the sensitivity required for the
determination
The lack of sensitivity at low oil content (<1%) is the main
limitation of the technique for the monitoring of residual oil
content. Furthermore, at 500C, the formation of pure coke
can distort the measures.
Despite its limitation, this method is a reference for a large
number of oil companies.
Results
1.

Characterization and quantification of pure

petroleum cuts
Seven industrial petroleum cuts or organic esters commonly
used in drilling muds formulations have been chosen and
analyzed by the laboratory Pollut-Eval analyzer. The table 1
presented below lists the compounds tested in this study.
reference
Ref 1
Ref 2
Ref 3
Ref 4
Ref 5
Ref 6
Ref 7
Ref 8

Composition
Industrial N paraffinic cut
Industrial N paraffinic cut /low aromatic content
Pure olefin cut
Industrial olefin cut
Industrial olefin cut
Industrial diesel oil cut
Industrial ester
Industrial ester (Ref 7) +
Industrial N paraffinic cut ( Ref 1)

Table 1: List of analyzed compounds

SPE 77472

Experimental
determination with sand
layers
75.7%
87.3%
67.95
93%
52.6%
83.6%
82.4%
88.3%

Table 2
In order to prevent the loss of the most volatile hydrocarbon
before the start of the analysis, all the above mentioned
hydrocarbons have been introduced in the crucible between 2
layers of cleaned adsorbent. The chemical adsorption of the
volatile compounds leads to much accurate results except for
some esters which molecular composition needs an adapted
calibration. As shown in the table 3, the mean percentages of
the hydrocarbon quantified are very close to the expected
theoretical values of 100%. The lower concentrations
obtained with the ester (Ref 7) are explained by their lower
carbon content. In that case, a specific calibration should be
applied for a better calibration.
In fact, the FID detection response based on carbon
estimation has to be normalized on hydrocarbon cut only for
hydrocarbon quantification. For base mud formulated with
ester, a precise quantification should take the ester of the
drilling mud formulations as reference.
reference

Theoretical
concentration

Ref 1
Ref 2
Ref 3
Ref 4
Ref 5
Ref 6
Ref 7
Ref 8

100%
100%
100%
100%
100%
100%
100%
100%

Table 3

Experimental
determination with
adsorbent layers
94.3%
94.2%
96.4%
94.4%
94.8%
93.1%
82.5%
90.5%

SPE 77472

POLLUT-EVAL: A NOVEL TOOL FOR DIRECT HYDROCARBON ANALYSIS IN CONTAMINATED SOILS

The initial and final temperatures were respectively 90C and

650C. The purpose of this study was to demonstrate the
good quantification of pure hydrocarbons by the method and
also to determine for each of them its specific pyrogram (see
figures 1 to 6). As shown in table 4, each hydrocarbon has
been characterized by its specific vaporization or cracking
temperature. For the Ref 1 and Ref 2 compounds, the
vaporization temperature are similar. This result was
expected because the only difference of these 2 hydrocarbon
cuts is their relative aromatic hydrocarbon content.
reference
Ref 1
Ref 2
Ref 3
Ref 4
Ref 5
Ref 6
Ref 7
Ref 8

Characteristic vaporization or cracking temperature

(C) between sand layers
194C 2C
196C 5C
150C 5C
231C 4C
172C 6C
189C 3C
305C 2C
184C4C / 274C4C

Table 4
The relative proportions of hydrocarbon detected in the 4
predefined temperature areas (noted Q0 to Q3) are closely
related to the carbon composition of the petroleum cuts
studied. The data obtained by the Pollut-Eval method and
presented below in table 5 have been correlated to the results
obtained after soil extraction and CPG analysis with precise
internal standard. (Figure 1 below)

Each petroleum cut is characterized by a specific

vaporization temperature with a good reproducibility but also
by its relative proportion in the 4 predefined areas (Q0,Q1,Q2
and Q3). Q1/Q2 areas correspond to C10/C40 carbon atoms.
For all of the hydrocarbon tested, the PC/COT ratios are close
to 1, revealing that the almost complete detection of these
compounds appear in 20 min during the first pyrolysis phase
before 650C.
This result leads to the conclusion that the oxidation phase is
useless to characterize such hydrocarbons.
For the 2 esters studied, the addition of an acid catalyser
before the analysis leads to a double peak due to the
hydrolysis of the ester before its vaporization. By this simple
test, the Pollut-Eval method is able to characterize and
quantify in a run of 20 min the presence of a low toxicity
ester in the drilling mud formulation.
As shown in the table 6 below, the method is also efficient to
quantify the relative proportion of 2 compounds (an ester and
a paraffinic cut) mixed in a formulation as used for offshore
applications. As shown in the table 6 below, the experimental
concentrations calculated are very close to the
theorical values.
reference
Compound 1
(ester)
Compound 2
(paraffinic cut)

Theoretical
concentration(%)
20

Experimental
determination (%)
18.5

80

81.5

Table 6
2.

Characterization and quantification of petroleum

cuts in drilling mud formulations.

The second step of this study was carried out to demonstrate

the ability of the method to characterize and quantify
petroleum cuts inside 3 industrial drilling mud commonly
used in the oil industry.
As shown in the table 7 below, the experimental
quantification compared to the expected values (real
concentrations prepared) is accurate.
reference

Type of
hydrocarbon

Theoretical
hydrocarbon
Concentration
(%p/p)

Experimental
hydrocarbon
quantification by
Pollut-Eval (% p/p)

Drilling
mud A
Drilling
mud B
Drilling
mud C

Ref 1
Paraffinic
Ref 7
Ester
Ref1
Paraffinic

42

463

46

420.1

43

431

Fig 1: CPG profile of pure diesel oil cut N6

reference

Relative
proportion
Q0(%)

Relative
proportion
Q1(%)

Relative
proportion
Q2(%)

Relative
proportion
Q3(%)

Ref 1
Ref 2
Ref 3
Ref 4
Ref 5
Ref 6
Ref 7
Ref 8

1.45
1.70
4.3
0.6
1.7
2.5
0
1.1

4.5
4.3
16.6
2.5
4.5
6.8
0.1
3

94
94
79
96.9
93.1
90.7
98.3
95.6

0
0
0
0
0.6
0
1.6
0.3

Table 5

Table 7
The natural organic matter detected (M.O) has been evaluated
by the method apart from the hydrocarbon concentrations. In
the 3 drilling muds studied, the Pollut-Eval method is able to
differentiate the hydrocarbon oil content of the drilling mud

YVES BENOIT

from its natural organic matter content. This part of the

carbon mass balance is included in the global TOC
determination (see table 8)
reference

Drillin
g mud
A
Drillin
g mud
B
Drillin
g mud
C

M.O
Natural
organic
matter
(g/kg)
1.3

TOC
Total
Organic
carbon
(%p/p)
38.6

Theoretical
hydrocarbon
Concentration
(%p/p)

Experimental
hydrocarbon
quantification by
Pollut-Eval
(% p/p)

42

463

SPE 77472

reference

Type of
hydrocarbon

Characteristic
pyrolysis cracking
temperature
(C)

Drilling
mud A
Drilling
mud C
Pure
paraffinic
cut

Ref 1

2029

Ref 1

2003

Ref 1

1942

Table 10
0.3

35.5

46

420.1

0.05

36.3

43

431

Table 8
During the weighting of the mud, the addition of an acid
catalyser in the crucible leads to the hydrolysis of the ester.
The method is able to determine if a low tox organic ester has
been put in the formulation.
Despite the 3 complex formulations and the presence of
various organic additives (emulsifier, viscosifier) or mineral
additives (bentonite, CaCl2, CaCO3, Nacl), no major
interference appeared.
As it was presented in the first part of this study, the
quantification of the hydrocarbon content in these 3 industrial
drilling mud formulations does not need the oxidation phase.
As shown below, the PC/TOC ratio are close to 1 (see Ref 9).
reference

Type of
hydrocarbon

PC/COT

Characteristic
pyrolysis cracking
temperature
(C)

Drilling
mud A
Drilling
mud B
Drilling
mud C

Ref 1
Paraffinic
Ref 7
Ester
Ref1
Paraffinic

0.99

2029

0.99

3134

0.98

2003

Table 9
Despite their own and different compositions, the specific
cracking temperatures of the hydrocarbon in drilling muds A
and C are similar. This result was expected because the
hydrocarbon cut ( base oil) in these 2 industrial formulations
is the same. No major interference due to any matrix effects
has altered the qualitative and quantitative results of the
method. Nevertheless, the characteristic vaporization
temperature of the paraffinic cut (ref1) analyzed as a pure
product compared to the one obtained in the drilling mud A
and C are slightly different as shown in the table 10 below.
Thus, the calibration should be done for better accuracy
within the complete drilling mud formulation.

3.

Characterization and quantification of hydrocarbon

in undersea discharged cuttings.

The last part of the study has been carried out on various
cuttings sampled near an offshore rig. The drilling operations
on this platform have generated great amounts of
contaminated drilling cuttings which were discharged into the
sea. Today, the OSPAR decision concerning the discharge of
OBM is limited to 1% of hydrocarbon. The determination of
the cuttings hydrocarbon content, many years after their
discharge, is of a great interest to evaluate their
environmental impact.
The knowledge of the pollution extension around offshore
rigs is also important if correlated to the microbiological and
biological recolonisation of the contaminated marine
sediment mixed with these cuttings.(Ref 3)
For these purpose, 5 years old discharged cuttings sampled
during an in-situ experimentation have been analyzed by the
Pollut-Eval method in order to determine their hydrocarbon
content compared to those obtained by solvent extraction and
gas phase chromatography. Discharged cuttings containing
paraffinic hydrocarbon cut (Ref 2) have been sampled at 180
m depth in various directions around the offshore rig.
The evaluation by the Pollut-Eval method of the hydrocarbon
concentration gradient in these marine sediments have been
evaluated from the discharge point of the cuttings, situated at
the feet of the rig, to 2000 m from the platform. This
procedure could be included in the site survey in order to
minimize environmental impact.
The table 11 presented below shows the comparison of the
hydrocarbon concentration determined by both analytical
techniques.

SPE 77472

POLLUT-EVAL: A NOVEL TOOL FOR DIRECT HYDROCARBON ANALYSIS IN CONTAMINATED SOILS

Distance and
direction from
the rig

Total hydrocarbon
concentration in the
cuttings by PollutEval Method
(% on dry matter)

Total hydrocarbon
concentration in the
cuttings by
Extraction/CPG
Method
(% on dry matter)

100 m through
south
230 m through
south
470 m through
south
730 m through
south
2000 m through
south
100 m through
west
180 m through
east

4.13 0.14

3.34 0.02

0.51 0.03

0.46 0.03

0.01

<0.05

<0.03

14.3 0.24

18.73 0.25

<0.4

Distance and
direction from
the rig
100 m through
south
230 m through
south
470 m through
south
730 m through
south
2000 m through
south
100 m through
west
180 m through
east

Total hydrocarbon
concentration in the
cuttings by PollutEval Method
(% on dry matter)
4.13 0.14

Natural organic
matter evaluated by
Pollut-Eval method
(% on wet matter)

0.51 0.03

0.09

0.01

0.10

0.10

0.12

14.3 0.24

0.05

0.12

0.08

Table 12

Table 11
For the quantitative comparison of the 2 methods, it is
important to note that the standardization of the CPG
response has been normalized with a recent hydrocarbon cut.
The evolution of the global hydrocarbon cut composition
after 4 years undersea could have a great influence on the
concentration calculated.
For the farthest samples in the south direction from the rig
(470, 730 and 2000m), the results of the 2 methods are in
good agreement and the hydrocarbon contents detected are
null or very low. In the framework of the OSPAR discharge
Guidelines in which discharged hydrocarbon content is
limited to 1%, the conclusions for both methods are similar.
Despite differences due to the intrinsic principle of both
methodologies and calibration, the conclusions for the
contaminated samples (100 m west and south) are similar:
these cuttings should not be discharged into the sea without
any pretreatment. The Pollut-Eval method has also been able
to evaluate the natural organic matter content of the non
contaminated sediments situated far from the rig (at 2000 m).
It is very interesting to note that the natural organic matter
content of the sediment is quite constant for the area tested,
even for the hydrocarbon contaminated one. For these
sediment and pollutant, the Pollut-Eval is able to differentiate
and evaluate the natural matter from light pollutant
hydrocarbon without severe interference.
These information should not be available from Retort Kit or
CPG methodologies.

As a qualitative point of view, the characteristic vaporization

temperatures obtained on the 3 contaminated samples are
presented below in table 13 and compared to the theoretical
value of the Ref 2 hydrocarbon cut introduced in the
drilling formulation.
Distance and
direction from the
rig

Total hydrocarbon
concentration in the
cuttings by PollutEval Method
(% on dry matter)

100 m through south

230 m through south
100 m through west

4.130.14
0.510.03
14.30.24

Theoretical Experimental
characteristic characteristic
vaporization vaporization
value
value
(C)
(C)

1965
1965
1965

211
193
219

Although the values are sufficiently similar to characterize

the Ref 2 cut, as noted before, an accurate calibration of the
vaporization temperature has to be determined within the
drilling formulation in order to take into account the matrix
effects revealed by these tests.
4.

Conclusions and discussion

With more and more stringent environmental regulations

concerning waste discharge, the oil companies will need
accurate and rapid analytical method to evaluate low oil
content before the discharge operations. The efficiency
control of treatment process such as thermal desorption or
reinjection of contaminated cuttings should be soon provided
.
Some techniques such as Retort Kit or Total organic carbon
determination by catalytic oxidation has been evaluated many
years ago and their lack of accuracy for low oil content
is obvious.

YVES BENOIT

CPG and IR, commonly used laboratory techniques, are

submitted to an expensive and time consuming extraction
pretreatment phase with Freon today prohibited.
The qualitative and quantitative results provided by the direct
Pollut-Eval method on pure hydrocarbon cuts but also on
drilling mud are encouraging.
Each of the hydrocarbon cut has been quantified with
accuracy and characterized with its average vaporization
temperature. This could be the starting point of a drilling mud
additive data base. For low tox compounds, a specific
calibration procedure should be applied, showing by the way
the
flexibility
of
the method.
The relative proportion of 2 organic cuts (ester mixed with nparaffin) have been detected with a good precision. The
addition of a low tox ester in the drilling mud could be
characterized by a simple test by the addition of an
acid catalyser.
The matrix effects observed on real cuttings for the
determination of vaporization temperature need further
investigations in order to define and qualify a more global
methodology which could be applied to various industrial
drilling mud formulations.
The Pollut-eval results compared to conventional techniques
have proved its efficiency to quantify low and high
hydrocarbon contents, despite complex formulations. On the
case studied, the accurate carbon mass balance provided is
able to differentiate natural or pollutant organic matter
detected in cuttings or sediments.
As conclusion, the method should be of a great use for site
survey, waste discharge treatment efficiency evaluation or
screening of any hydrocarbon contaminated solid waste
(ref4).
Furthermore, this technique could be easily included in the
monitoring of the mud (on line), and does not require the
carriage of samples in a specialized laboratory.
Acknowledgements
Our special thanks to OLEON for providing esters, to
IFREMER and TFE for providing cuttings.
Thanks to P. Le Minter and I. Focquenoey for performing
these experiments and availability.
References.
1.

2.

3.

S. Saintpere, A. Morillon-Jeanmaire: "Measuring very

low oil content on cuttings: A challenging approach of
the Zero OPF discharge option", SPE 61096,Norway 2628 June 2000
J.Ducreux & Al: "Utilisation de la mthode Rock-Eval
pour lvaluation des sols contamins par des composs
hydrocarbons", Analusis Magasine, 1997, V. 25, N910.
D.Blanchet, R.Camps, C.Damazzone, E.Dutrieux,
J.Durrieu, E.His, P.Le Minter, J.Seria, F.Galgani,

4.

SPE 77472

"Toxicity and recolonization of drill cuttings- A french

experiment.", SPE 77471, to be presented at SPE ATCE
San Antonio 2002.
J.Espitali, IFP: "Mthode rapide danalyse gochimique
des dblais en suivi deforage",Ptrole et Techniques N
283- Octobre 1981.

SPE 77472

POLLUT-EVAL: A NOVEL TOOL FOR DIRECT HYDROCARBON ANALYSIS IN CONTAMINATED SOILS

PYROLYSIS PROFILE OF PURE HYDROCARBON

CUTS
USED
IN
DRILLING
MUD
Pyrolysis profile of the Paraffinic cut (Ref1)
300 000

700

Q0

Q1

Q3

Q2
192C

600

500
200 000
400

FID
[pA]

300
100 000
200

100

0
0

10

20
Time [min]

FID

FID
[pA]

Pyrolysis profile of an ester (Ref7)

350 000

700

Q0

Q2

Q1

Q3

306C

300 000

600

250 000

500

200 000

400

150 000

300

100 000

200

50 000

100

T
[
C]

0
0

10

20
Time [min]

FID

FID [pA]

Pyrolysis profile of an Olefin cut (Ref 3)

400 000

700

Q0
350 000

Q2

Q1

Q3

154C

600

300 000

500

250 000
400
200 000
300
150 000
200

100 000

100

50 000

0
0

10

20
Temps [mn]

FID

T
[
C]

T
[
C]

10

YVES BENOIT

SPE 77472

Pyrolysis profile of an Hydrolysed Ester

700

Q0

Q1

Q3

Q2
351C

600

FID [pA]
500

478C

400

100 000
300

200

100

0
0

10

20
Time [min]

FID

Pyrolysis profile of the Mixture composed of a Paraffinic cut and an Ester

300 000

700

Q0

Q1

180C

Q2

Q3
600

500

parrafinic cut

Temperature gradient of
25C/min

200 000

400

FID
[pA]

300
100 000

270

200

Ester

100

0
0

10

20
Time [min]

FID

Pyrolysis profile of a diesel oil cut (Ref 6)

200 000

700

Q0
FID
[pA]

Q1

Q2

Q3
600

500

186C

400
100 000
300

200

100

0
0

10

20
Time[mn]

FID

T
[
C]

T
[
C]

T
[
C]

SPE 77472

POLLUT-EVAL: A NOVEL TOOL FOR DIRECT HYDROCARBON ANALYSIS IN CONTAMINATED SOILS

11

PYROLYSIS PROFILE OF DRILLING MUD

CONTAINIG INDUSTRIAL HYDROCARBON CUT
DRILLING MUD FORMULATED WITH PARAFFINIC HYDROCARBON CUT (Ref 1)
700
Q0

Q2

Q1

Q3
600

200C

200 000

400
T [C]

FID Detection[pA]

500

300

100 000

200

100

0
0

10

20

30

Time [mn]
FID

DRILLING MUD FORMULATED WITH A LOW TOX ESTER (Ref 7)

700
300 000

Q0

Q1

Q2

Q3
600
311C

200 000
400
T [C]

FIDDetection [pA]

500

Ester
300
100 000

Natural organic matter

200

100

0
0

10

20
Time[mn]
FID

30

12

YVES BENOIT

SPE 77472

DRILLING MUD A FORMULATED WITH N-PARAFFINIC HYDROCARBON CUT (ref 1)

700

Q0

Q2
196C

Q1

Q3
600

N-PARAFFINIC HYDROCARBON

200 000

500

T [C]

FID [pA]

400

300
100 000

NATURAL ORGANIC MATTER

200

100

0
0

10

20
Temps [mn]

FID

PYROLYSIS PROFIL OF CONTAMINATED

DRILLING CUTTINGS
CONTAMINED CUTTINGS SAMPLED AT 100 M WEST FROM THE RIG
300 000

700

Q0

Q1

Q2

Q3
600

HYDROCARBON CUT

500

400
T [C]

FID Detection [pA]

200 000

300

NATURAL ORGANIC
MATTER

100 000

200

100

0
0

10

20

30

Time [mn]

FID

CONTAMINATED CUTTINGS SAMPLED AT 100 M SOUTH FROM THE RIG

50 000

700

Q0

Q1

Q2

Q3
600

40 000

30 000

400
T [C]

FID DETECTION [pA]

500

HYDROCARBON
CUT

300

20 000

NATURAL ORGANIC MATTER

200
10 000
100

0
0

10

20
TIME [mn]

FID

30