-
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. This paper was selected for presentation by an SPE
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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 n-paraffin, 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 post-treatment 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
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.
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2 YVES BENOIT SPE 77472
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. 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
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 Pollut-Eval 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
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
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SPE 77472 POLLUT-EVAL: A NOVEL TOOL FOR DIRECT HYDROCARBON
ANALYSIS IN CONTAMINATED SOILS 3
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
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4 YVES BENOIT SPE 77472
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. 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 (
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SPE 77472 POLLUT-EVAL: A NOVEL TOOL FOR DIRECT HYDROCARBON
ANALYSIS IN CONTAMINATED SOILS 5
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 Characteristic vaporization or cracking temperature
(C) between sand layers Ref 1 194C 2C Ref 2 196C 5C Ref 3 150C
5C Ref 4 231C 4C Ref 5 172C 6C Ref 6 189C 3C Ref 7 305C 2C Ref 8
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)
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 1.45 4.5 94 0 Ref 2 1.70 4.3 94 0 Ref 3 4.3 16.6 79
0 Ref 4 0.6 2.5 96.9 0 Ref 5 1.7 4.5 93.1 0.6 Ref 6 2.5 6.8 90.7 0
Ref 7 0 0.1 98.3 1.6 Ref 8 1.1 3 95.6 0.3
Table 5
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 Theoretical concentration(%)
Experimental determination (%)
Compound 1 (ester)
20 18.5
Compound 2 (paraffinic cut)
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
Ref 1 Paraffinic
42 463
Drilling mud B
Ref 7 Ester
46 420.1
Drilling mud C
Ref1 Paraffinic
43 431
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
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6 YVES BENOIT SPE 77472
from its natural organic matter content. This part of the carbon
mass balance is included in the global TOC determination (see table
8) reference M.O
Natural organic matter (g/kg)
TOC Total
Organic carbon (%p/p)
Theoretical hydrocarbon
Concentration (%p/p)
Experimental hydrocarbon
quantification by Pollut-Eval
(% p/p)
Drilling mud
A
1.3 38.6 42 463
Drilling mud
B
0.3 35.5 46 420.1
Drilling mud
C
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
Ref 1 Paraffinic
0.99 2029
Drilling mud B
Ref 7 Ester
0.99 3134
Drilling mud C
Ref1 Paraffinic
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.
reference Type of hydrocarbon
Characteristic pyrolysis cracking
temperature (C)
Drilling mud A
Ref 1
2029
Drilling mud C
Ref 1 2003
Pure paraffinic
cut
Ref 1 1942
Table 10
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.
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SPE 77472 POLLUT-EVAL: A NOVEL TOOL FOR DIRECT HYDROCARBON
ANALYSIS IN CONTAMINATED SOILS 7
Distance and
direction from the rig
Total hydrocarbon concentration in the cuttings by Pollut-
Eval Method (% on dry matter)
Total hydrocarbon concentration in the
cuttings by Extraction/CPG
Method (% on dry matter)
100 m through south
4.13 0.14 3.34 0.02
230 m through south
0.51 0.03 0.46 0.03
470 m through south
0.01
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8 YVES BENOIT SPE 77472
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 n-paraffin) 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.
S. Saintpere, A. Morillon-Jeanmaire: "Measuring very
low oil content on cuttings: A challenging approach of the Zero
OPF discharge option", SPE 61096,Norway 26-28 June 2000
2. J.Ducreux & Al: "Utilisation de la mthode Rock-Eval pour
lvaluation des sols contamins par des composs hydrocarbons",
Analusis Magasine, 1997, V. 25, N9-10.
3. D.Blanchet, R.Camps, C.Damazzone, E.Dutrieux, J.Durrieu,
E.His, P.Le Minter, J.Seria, F.Galgani,
"Toxicity and recolonization of drill cuttings- A french
experiment.", SPE 77471, to be presented at SPE ATCE San Antonio
2002.
4. J.Espitali, IFP: "Mthode rapide danalyse gochimique des
dblais en suivi deforage",Ptrole et Techniques N 283- Octobre
1981.
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SPE 77472 POLLUT-EVAL: A NOVEL TOOL FOR DIRECT HYDROCARBON
ANALYSIS IN CONTAMINATED SOILS 9
PYROLYSIS PROFILE OF PURE HYDROCARBON CUTS USED IN DRILLING
MUD
Pyrolysis profile of the Paraffinic cut (Ref1)
0
100 000
200 000
300 000
0 10 20
Time [min]
FID[pA]
0
100
200
300
400
500
600
700
T[C]
FID T
Q0 Q1 Q2 Q3
192C
Pyrolysis profile of an ester (Ref7)
0
50 000
100 000
150 000
200 000
250 000
300 000
350 000
0 10 20
Time [min]
FID[pA]
0
100
200
300
400
500
600
700
T[C]
FID T
Q0 Q1 Q2 Q3306C
Pyrolysis profile of an Olefin cut (Ref 3)
0
50 000
100 000
150 000
200 000
250 000
300 000
350 000
400 000
0 10 20Temps [mn]
FID [pA]
0
100
200
300
400
500
600
700
T[C]
FID T
Q0 Q1 Q2 Q3154C
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10 YVES BENOIT SPE 77472
Pyrolysis profile of the Mixture composed of a Paraffinic cut
and an Ester
0
100 000
200 000
300 000
0 10 20
Time [min]
FID[pA]
0
100
200
300
400
500
600
700
T[C]
FID T
Q0 Q1 Q2 Q3180C
270
parrafinic cut
Ester
Temperature gradient of25C/min
Pyrolysis profile of a diesel oil cut (Ref 6)
0
100 000
200 000
0 10 20
Time[mn]
FID[pA]
0
100
200
300
400
500
600
700
T[C]
FID T
Q0 Q1 Q2 Q3
186C
Pyrolysis profile of an Hydrolysed Ester
0
100 000
0 10 20
Time [min]
FID [pA]
0
100
200
300
400
500
600
700
T[C]
FID T
Q0 Q1 Q2 Q3351C
478C
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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)
0
100 000
200 000
0 10 20 30
Time [mn]
FID
Det
ectio
n[pA
]
0
100
200
300
400
500
600
700
T [
C]
FID T
Q0 Q1 Q2 Q3
200C
DRILLING MUD FORMULATED WITH A LOW TOX ESTER (Ref 7)
0
100 000
200 000
300 000
0 10 20 30
Time[mn]
FID
Det
ectio
n [p
A]
0
100
200
300
400
500
600
700
T [
C]
FID T
Q0 Q1 Q2 Q3
311C
Ester
Natural organic matter
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12 YVES BENOIT SPE 77472
PYROLYSIS PROFIL OF CONTAMINATED
DRILLING CUTTINGS
DRILLING MUD A FORMULATED WITH N-PARAFFINIC HYDROCARBON CUT (ref
1)
0
100 000
200 000
0 10 20Temps [mn]
FID
[pA]
0
100
200
300
400
500
600
700
T [
C]
FID T
Q0 Q1 Q2 Q3196C
N-PARAFFINIC HYDROCARBON
NATURAL ORGANIC MATTER
CONTAMINED CUTTINGS SAMPLED AT 100 M WEST FROM THE RIG
0
100 000
200 000
300 000
0 10 20 30
Time [mn]
FID
Det
ectio
n [p
A]
0
100
200
300
400
500
600
700
T [
C]
FID T
Q0 Q1 Q2 Q3
HYDROCARBON CUT
NATURAL ORGANIC MATTER
CONTAMINATED CUTTINGS SAMPLED AT 100 M SOUTH FROM THE RIG
0
10 000
20 000
30 000
40 000
50 000
0 10 20 30
TIME [mn]
FID
DET
ECTI
ON
[pA
]
0
100
200
300
400
500
600
700
T [
C]
FID T
Q0 Q1 Q2 Q3
HYDROCARBON CUT
NATURAL ORGANIC MATTER
