SPE 94604

One-Step Acid Removal of an Invert Emulsion

L. Quintero, SPE, T. J ones, SPE, and D.E. Clark, SPE, Baker Hughes Drilling Fluids
Copyright 2005, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE European Formation Damage
Conference held in Scheveningen, The Netherlands, 25-27 May 2005.

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Abstract
Removal of skin damage resulting from internal and external
filter cake deposition during oil well reservoir drilling with
invert emulsion drill-in fluid is desirable in order to maximize
hydrocarbon recovery. Efficient filter cake cleanup is required
for a number of open-hole completion operations, including
the use of stand-alone and expandable sand screens, and
conventional gravel pack applications for both production and
water-injection wells.
Most of the currently used chemical methods to remove
invert emulsion filter cake and internal formation damage are
based on the use of acids, solvents and mutual solvents mixed
in clear brine. Completing a well after drill-in with emulsion-
based fluids is time-consuming and costly, and usually
involves large volume multi-stage soak treatments.
Surfactant technology, when appropriately combined with
conventional acid, allows a single-stage invert emulsion
cleanup process. In this one-step cleanup method, the invert
emulsion filter cake is incorporated into the organized
surfactant in solution and the acid-soluble particles are then
decomposed.
A number of injection permeability tests were performed
on Berea sandstone cores and ceramic discs using various
invert emulsion drilling fluids for filter cake deposition and
organized surfactant in solution/acid blends for filter cake
removal. This investigation demonstrated that, when using this
technology to destroy the filter cake, (1) the invert emulsion is
incorporated into the surfactant solution, (2) the solids become
water-wet, (3) sludge formation between the acid and invert
emulsion cake is prevented, and (4); and the majority of acid-
soluble particles are removed.
This approach appears to be a credible method for
removing formation skin damage and increasing hydrocarbon
recovery and/or water injection rates.

Introduction
Many operators are interested in improving filter cake cleanup
after drilling into reservoirs with invert emulsion drilling
fluids. More efficient filter cake cleanup is desired for a
number of open hole completions, including stand-alone and
expandable sand screens, as well as for gravel pack
applications for both production and water injection wells.
One-step invert emulsion filter cake cleanup technology
uses a single-phase microemulsion (SPME)
1-3
and
conventional acid packages, in a single blend, to solubilize the
oil into the SPME, reverse the wettability of the filter cake
solids, and simultaneously decompose its acid-soluble
components. Reversing the wettability of the filter cake, using
surface active chemistry, facilitates acidizing by preventing a
sludge that could form between the acid and the emulsified
cake and by making acid-soluble particles unavailable to
unspent acid.
Besides the advantage of reduced skin damage, increased
hydrocarbon recovery and/or increased water injection rates, a
one-step near wellbore cleanup method will save an
operator valuable rig time.

Theory of Microemulsion
In the 1950s, Schulman and co-workers added alcohol to
surfactant-stabilized oil-in-water (o/w) emulsions to obtain
very stable homogeneous fluids that he called
microemulsions.
4
These microemulsions had an average
droplet size of 10-100 nanometers (nm), much smaller than
conventional emulsions.
The first studies of microemulsions in the oil industry were
in the 1970s for enhanced oil recovery (EOR) applications.
5-11

Many oil operators and universities invested considerable time
to research this topic. The research group led by Schechter and
Wade at The University of Texas at Austin made important
contributions to the understanding of the mechanism of
increased production by microemulsions. However, the
interest dropped due to the crude oil price decrease and
because the technology was expensive, due mainly to the high
concentration of surfactant required. Since then, the oil
industry has conducted only a small amount of research on
microemulsions.
In the past 25 years, surfactant manufacturers, universities
and research institutes have greatly increased the knowledge
of microstructures and the phase behavior of microemulsions,
and have made surfactants available that are more efficient for
microemulsion formulations.
12-18
A microemulsion is a thermodynamically-stable complex
fluid typically composed of a non-polar oil phase, a polar
2 SPE 94604
water phase, surfactant and an optional co-surfactant. They are
macroscopically homogeneous and, at the microscopic level,
heterogeneous, consisting of individual domains of the non-
polar oil phase and polar water phase, separated by a
monolayer of surfactant (amphiphile).
1, 2, 14, 15
Microemulsions
are typically clear solutions, as the droplet diameter of the
organized phase is approximately 100 nm or less, and contain
two immiscible fluids, in contrast to micellar solutions, which
are considered to be one-phase fluids and may be either water
or oil. The schematic in Figure 1 shows the difference
between micelles and microemulsions.
The surfactant molecules in these microemulsion fluids
lower the interfacial free energy to very nearly zero, which
induces the spontaneous microemulsification when the
components are brought together. These fluids may be oil-in-
water, water-in-oil, or a single-phase microemulsion with bi-
continuous structure. The schematic representation of phase
transition of oil/water/surfactant system according to Winsor
definition is show in Figure 2. Winsor I is formed by oil-
swollen micelles in equilibrium with excess oil (i.e. two
phases, with the surfactant in the lower phase). Winsor II is
formed by water-swollen reverse micelles in equilibrium with
excess water. Winsor III is a middle-phase microemulsion,
with excess water and oil. Winsor IV is a single-phase
microemulsion.
1, 2, 19
For O/W microemulsion, the water diffusion is rapid,
while the oil diffusion is low, and its diffusion process is
dominated by the diffusion of the oil-swollen micelles. In the
case of bicontinous microemulsions, both components are
expected to diffuse rapidly, having self-diffusion coefficients
close to the values of the neat liquids, which suggested that
some continuity must exist between the water and the oil
domains.
1, 20

Laboratory tests
A concentrated SPME that contains water, a solvent, a
surfactant blend and a co-surfactant, was diluted in calcium
chloride brine and used as a soak solution to remove oil-based
drilling fluid filter cake. The soak solution was also
formulated in an acidic media, which was designed to dissolve
the bridging particles in the filter cake.
The concentration of SPME in the brine was selected by a
series screening tests whereby the criteria was to incorporate
all of the oil in the filter cake into the soak solution and
change the wettability of the solids from oil-wet to water wet.
Sandpack and Hassler Permeameters were used to evaluate
the efficiency of the soak solution to remove the filter cake
and the oil from the invert emulsion fluid filtrate. A schematic
diagram of the Sandpack and Hassler Permeameters are shown
in Figures 3 and 4. The Sandpack Permeameter tests were run
using 20-micron discs (2800 mD), 140/270 sand and 40/60
gravel. The tests in the Hassler cell were run using one-inch
diameter Berea sandstone plugs with a range of permeabilities.
The cleanup tests were performed using filter cakes
obtained from oil-based drilling fluids formulated either with
barite, calcium carbonate or a barite/calcium carbonate blend.
The oil-base drilling fluid used was a 10 lb/gal system with a
65/35 oil/brine ratio. The properties of the fluid formulated
with a blend of barite and calcium carbonate are given in
Table 1.
The filter cake cleanup evaluation was based on water
injection permeability. Injection tests were chosen instead of
production permeability tests because injection is considered a
worst case scenario, from the viewpoint of return
permeability. The test procedure begins with the measurement
of the initial, baseline permeability to injection brine
consisting of filtered synthetic seawater. Next, a filter cake is
deposited on a ceramic disc or Berea sandstone, followed by
treatment with the soak solution for a specified period of time.
The mud-off time for deposition of the filter cake ranged from
1 to 4 hours. The soak time for the tests was in the range from
2 to 16 hours. The last step of the procedure is the water
injection measurement to determine the final injection
permeability.

Results and Discussion
Single phase microemulsion evaluation
A microemulsion or other surfactant system could be altered
as the water/solvent/surfactant system changes, from Winsor
I Winsor II Winsor III Winsor IV, by changing
parameters such as salinity and water/solvent ratio. Therefore,
the textures of the SPME were examined under a polarized
microscope in order to detect the existence of typical lamellar
structures that co-exist with the microemulsions in a phase
diagram of water/solvent/surfactant system. Figure 5a shows
photographs of the SPME under polarized light. The
photographs depict a lamellar phase with associated oily
streaks.
21
This type of structure coexists with the bicontinuous
phases of the concentrated SPME. Dilution of the SPME in
high-salinity brine is shown by Maltese crosses dispersed in a
bi-refrigent matrix, indicating that the behavior of the SPME
has not shifted after the dilution. (Figure 5b)
To verify that the SPME remained as a microemulsion
after the acid package addition, a compatibility test utilizing
SPME with acid was evaluated with microemulsion
concentrations up to 30% in brine and with various acids at
concentrations between 5 and 7.5%. Visual observation allows
one to determine whether or not fluid compatibilities exist. For
example, when a microemulsion blend remains as a clear
single phase, this indicates that the fluids are compatible.
Observation of phase separation and cloudiness indicates an
incompatibility with acid. Figure 6 shows a photograph of
single-phase microemulsion with acid. The vial on the left side
illustrates the behavior of a microemulsion that separates,
showing a typical Winsor II behavior with water-swollen
reverse micelles in equilibrium with a water phase. The vial on
the right side illustrates the behavior of a microemulsion that
remains stable as a SPME. This typical behavior results from
the effect of the acid on the anionic or cationic surfactants
used in microemulsions. The use of nonionic surfactants, such
as the one used in the example of SPME 2 of Figure 6,
prevents this type of acid/microemulsion incompatibility.

Cleanup of filter cake with SPME in brine
The first part of the filter cake cleanup study included a series
of screening tests with the SPME in brine and no acid in the
formulation. The injection permeability tests were performed
on ceramic discs in a Sandpack permeameter. A cake
deposition time of one-hour at 150F and 500 psi was used to
obtain a filter cake with a reasonable thickness to break in
SPE 94604 3
order to verify the SPME efficacy. The soak solution,
containing 10% SPME mixed with a 10 lb/gal CaCl2 brine,
was allowed to soak at 150F and 200 psi for up to 2 hours.
Upon contact of the soak solution with the filter cake, the soak
destabilized the invert emulsion and penetrates the filter cake,
as shown in Figures 7a, 7b, and 7c. The results shown in
Figure 7b demonstrate that the 10% SPME soak solution in
10 lb/gal CaCl2 works to completely destroy the emulsion
contained in a 1-hr filter cake. The remaining filter cake
residue was altered to a water-wet condition to the point that it
could be easily decanted from the test cell after soaking and
before water injection. Figure 7c is a photo of the filter cake
remains after a soak treatment, decantation and water
injection. In the case of an invert emulsion system formulated
with barite only and treated with the SPME, the filter cake
particles became water-wet, slurrified and very porous as
shown in Figure 8.
Table 2 shows the results of the injection return
permeability tests. In the case of a vertical cell set-up, the
altered filter cake remained in place, as it cannot be displaced
due to equipment limitation. However, the filter cake was very
porous and loosely consolidated and, as a result, it was
possible to obtain a high percentage of water injection
(97.7%). In the case of horizontal cell setup, the disturbed
filter cake was easily displaced, and the percentage water
injection was 106%.

One-step cleanup of filter cake: SPME with acid in brine
The second part of the filter cake cleanup study was the
evaluation of the one-step soak formulation, an SPME in
conjunction with an acid package in brine. A number of
laboratory tests were performed using SPME together with
various types of acid treatments on invert emulsion filter
cakes.
Injection permeability tests in the Sandpack Permeameter
Injection permeability tests were performed on ceramic discs
in a Sandpack permeameter.
The first phase of the tests consisted of filter cake
deposition on a 20 m ceramic disc. Next, the filter cake was
exposed to a SPME containing acid for 4 hours.
Figure 9 shows the injection permeability results after 2-hr
mud-offs and 4-hr soak times using 10 lb/gal OBM and a soak
solution formulated with 30% SPME and 7.5% HCl in 9 lb/gal
CaCl
2
brine. The injection return permeability was 103.6%
and, after the test, the ceramic disc with the filter cake shows
that the acid-soluble particles were removed and only a small
amount of barite is observed. Figure 10
Table 3 shows the result of tests where the invert emulsion
filter cake, formulated either with calcium carbonate or
barite/calcium carbonate exposed to a blend of the SPME and
acid in 10 lb/gal CaCl
2
brine. The result indicates that the
combination of SPME and acid, either acetic acid or
hydrochloric acid, gave water injection return permeability
results greater than 100%. It is believed that the >100%
results are due to the reduced interfacial tension of the
injection fluid arising from (1) the additives surfactants in the
acid package, and (2) the single phase microemulsion.

Injection permeability tests in the Hassler Permeameter
Tests were also conducted in a Hassler Permeameter using
Berea Sandstone. The mud-off time of these tests was 16 hrs,
and the filter cake was flushed with base oil at 200 psi, to
simulate a wellbore displacement to remove the excess oil
from the external filter cake. The SPME concentration was
15% in 10 lb/gal CaCl
2
containing 10% Acetic Acid and the
soak time was 2 hours. Table 4 shows the results of these
return injection permeability tests. The first test was only a
simple injection test. Test 2, was divided into two parts. Part
I (Test 2a) was an injection test performed using the exact
procedures used in the first test. Part II (Test 2b) incorporated
a water injection step, but in the production direction,
followed by a second injection in the original direction. These
results demonstrate that there is value in producing the filter
cake first and then re-injecting. However, the original
injection results, without production flow, also gave very good
results.

The effects of mud-off time and calcium carbonate loading
It has been demonstrated in previous laboratory testing that
long mud-off times have significant (negative) effects on
permeability, especially if a static filter cake is allowed to
form over long periods of time. If a static filter cake is
allowed to build during field applications, high rate
displacements are pumped to reduce the static filter cake
thickness.
A series of static tests were performed on a Sandpack
Permeameter using different calcium carbonate loadings. For
each test, the cake deposition time, prior to the second water
injection permeability measurement, was 2 to 3 hours. The
results presented in Table 5 show that an increase in mud-off
time resulted in a reduction of injection permeability from
84.3% to 48.2% for an OBM system with high concentration
of calcium carbonate (Tests 1 and 2). However, the increase in
soak time from 2 to 16 hours generated a high percentage
increase in water injection (from 67.3% to 90.3%).

Conclusion
1. One-step invert emulsion filter cake cleanup was
efficiently achieved using SPME and acid blends in brine.
2. The injection permeability test results prove that the
SPME cleanup technique partially removes OBM and
OBM filter cakes, water-wets the solid particles and
avoids sludge formation.
3. The invert emulsion system with barite treated with the
single-phase microemulsion resulted in a loose, porous
filter cake that may be easily displaced.
4. The high injection permeability tests results with invert
emulsion systems formulated with barite, calcium
carbonate or combinations of barite and calcium
carbonate proves that the one-step filter cake cleanup
technique is effective for variations in fluid formulations.
5. A 15-30% single-phase microemulsion, with an acid in
brine, incorporated the oil phase of an OBM filter cake
into the aqueous soak solution and acidized the calcium
carbonate in one step.
6. Because invert emulsion systems are the drill-in fluids of
choice to drill pressure depleted reservoirs in many global
operations, the SPME technology presented in this paper
4 SPE 94604
appears to be an excellent approach to remove near
wellbore damage for water injection applications.

References
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185.
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Promod Kumar and K. L. Mittal, Marcel Dekker, Inc, New York
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Topology of Phase Boundaries for Oil/Brine/Surfactant Systems
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(1981) 28.
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Vasquez, E., Optimum Formulations of Surfactant/Oil/Water
Systems for Minimum Tension and Phase Behavior, Soc.
Petrol. Eng. J., 19, (1979) 107.
7 Biais, J., Bothorel, P., Clin, B., and Lalane, B., Theorical
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Properties and Role of Alcohol, J. Dispersion Sci and Technol.,
2, 1 (1981) 67.
8 Scriven L. E., Equilibrium Bicontinuous Structure, Nature,
263, (1976) 123.
9 Graciaa, A., Lachaise, J., Sayous, J. G., Grenier, P., Yiv, S.,
Schecter, R. S., and Wade, W. H., The Partioning of Complex
Surfactant Mixture between Oil/Water/Microemulsion Phases at
High Surfactant Concentrations, J. Colloid Interfase Sci., 93, 2,
(1983) 474.
10 Reed, R.L., and Healy, R.N., Physicochemical Aspects of
Microemulsion Flodding: A Review, in Improved Oil Recovery
by Surfactant and Polymer Flooding, ed by Shah D. O.,
Schechter R.S., Academic Press, New York (1977) 383.
11 Neogi, P., Oil Recovery and Microemulsions in
Microemulsion: Structure and Dynamics, ed by S. E. Friberg
and P. Bothorel, CRC Press, Inc., Boca Raton, Florida (1987)
197.
12 Prince, L. E., Microemulsions in Emulsions and Emulsions
Technology Part I, Surfactant Science Series, ed by Kenneth J.
Lissant, Marcel Dekker, Inc, New York (1974) 125.
13 Auvray, L., Cotton J.P., Ober, R., and Taupin, C., Evidence for
Zero Mean Curvature Microemulsions, J. Physical Chemistry,
88, (1984) 4584.
14 Bohlen, D. S., Vinson, P. K., Davis H. T., Scriven, L. E., Xie,
M., Zhu, X., and Miller, G.W., Generic patterns in the
Microstructure of Midrange Microemulsions in Organized
Solutions, Surfactant Science Series, ed by S. E. Friberg and B.
Lindman, Marcel Dekker, Inc, New York, (1992) 145.
15 Zana, R., and Lang, J., Dynamic of Microemulsions in
Microemulsion: Structure and Dynamics, ed by S. E. Friberg
and P. Bothorel, CRC Press, Inc., Boca Raton, Florida (1987)
153.
16 Holmberg, K., Quarter Century Progress and New Horizonts in
Microemulsions in Micelles, Microemulsion, and Monolayers,
Science and Technology, ed. by D.O. Shah, Marcel Dekker, Inc,
New York, (1998) 161.
17 Pursley, J. T., Penny, G., Microemulsion Additives Enable
Optimized Formation Damage Repair and Prevention, SPE
86556, presented at the 2004 International Symposium on
Formation Damage Control, Febreuary 18-20.
18 Chan; Albert F.; Bohon; William Mark ; Blumer; David J. ; Ly;
Kieu T.; Surfactant composition for cleaning wellbore and oil
field surfaces using the surfactant composition, US 6,130,199,
October 10, 2000.
19 Winsor, P.A., Solvent Properties of Amphiphilic Compounds,
Butterworth, London, 1954.
20 Olsson, U. and Lindman B.; Uni- and Bicontinuos
Microemulsions, in The Structure, Dynamics and Equilibrium
Properties of Colloidal Systems, ed by D. M. Bloor and E. Wyn-
Jones, Kluwer Academic Publishers, Netherlands (1990) 233.
21 Bellocq, A. M.; Effect of Alcohol Chain Length and Salt on
Phase Behavior and Critical Phenomena in SDS
Microemulsions, in Handbook of Microemulsion Science and
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Acknowledgments
The authors would like to thank Baker Hughes Drilling Fluids
for allowing us to publish this paper. Special thanks are in
order to the laboratory personnel that generated data
supporting development of this technology.

SI Metric Conversion factors
psi x 6.894 757 E +03 = pa
cP x 1.08* E -03 = Pa.s
mL x 1.0* E -06 = m
3
mD x 9.869 233 E -16 = m
2
m

x 1.0* E -06 = m
lbf/100 ft
2
x 0. 478 803 E 00 = Pa
lb/gal x 1.198 264 E +02 = kg/m
3
F (F-32)/1.8 = C
in. x 2.54* E +00 = m
* Conversion factor is exact.
Tables
Table 1 Rheological and filtration properties of the
drilling fluid formulation
Properties
Mud weight, lb/gal 10
O/W ratio 65/35
Plastic viscosity, cP 18
Yield point, lbf/100 ft
2
12
3-rpm reading 6
10-sec gel, lbf/100 ft
2
8
Spurt, mL/30 min 0.4
Total filtrate,mL/30 min 2.8

SPE 94604 5

Table 2 Return injection permeability using 30% SPME in 9 lb/gal CaCl
2
brine as cleanup soak
Permeability Mud-off time/
Soak time, hrs
Test
set-up
Drilling fluid
Initial,
mD
Final,
mD
Injection
permeability, %
2/4 Vertical 10 lb/gal OBM with
barite
82.5 80.4 97.7
2/4 Horizontal 10 lb/gal OBM with
barite
80 84.8 106



Table 3 Return injection permeability using one-step cleanup soak in the Sandpack Permeameter
Test set-up: Vertical Cell Position
Permeability Mud-off time/
Soak time, hrs
10 lb/gal Soak
solution
10 lb/gal
Drilling fluid
Initial,
mD
Final,
mD
Injection
perm, %
2/4 15% SPME and 10%
acetic acid
OBM with
CaCO
3
180.8 194.9 107.8
2/4 30% SPME and 10%
acetic acid
OBM with
CaCO
3
304.1 588 193.3
2/4 30% SPME and 7.5%
hydrochloric acid
OBM with barite
+CaCO
3
696.7 722 103.7



Table 4 Return injection permeability using one-step cleanup soak in the Hassler Permeameter 16-hr mud off
Soak solution: 15% SPME and 10% acetic acid in 10% CaCl
2
Permeability
Test
Drilling fluid
Initial, mD Final, mD % Injection
permeability
1
10 lb/gal OBM with CaCO
3
2364 2017 mD 85.3 %
2a
10 lb/gal OBM with CaCO
3
1323 mD 1150.9 mD 86.9 %
2b*
10 lb/gal OBM with CaCO
3
1323 mD 1326 mD 100.3 %
*: Test 2b included a water flow in the production direction after the first injection test (Test 2a) and
before re-injecting water in the injection direction. No additional soaking was done.



Table 5 Effect of time on injection permeability using one-step cleanup soak in the Sandpack Permeameter
Soak solution: 15% SPME and 10% acetic acid in 10% CaCl
2
Permeability
Test Mud-off time/
Soak time, hrs
CaCO
3
in
OBM, lb/bbl
Initial,
mD
Final,
mD
Injection
permeability, %
1 2/2 128 230.5 194.3 84.3
2 3/2 128 95.3 45.9 48.2
3 3/2 50 179.8 121.0 67.3
4 3/16 50 239.7 216.4 90.3

6 SPE 94604
Figures


Figure 1 Schematic representation of micelles and microemulsions






Figure 2 Phase transition of oil/water/surfactant system according to Winsor definition


SPE 94604 7

Figure 3 Sandpack Permeameter






Figure 4 Hassler Permeameter







8 SPE 94604


Figure 5 Optical textures observed in the single phase microemulsion




Figure 6 Compatibility of SPME with acid





Figure 7 Invert emulsion filter cake cleanup with SPME in CaCl
2
brine







SPE 94604 9


Figure 8 Barite filter cake cleanup with SPME in CaCl
2
brine



Init. Inj Perm
696.7 mD
Final Inj Perm
722 mD
% Injection Permeability = 103.6
Figure 9 Injection return permeability after one-step filter cake cleanup



Figure 10 Invert emulsion filter cake cleanup with SPME and hydrochloric acid in CaCl
2
brine