3rd AMIREG International Conference (2009): Assessing the Footprint of 53

Resource Utilization and Hazardous Waste Management, Athens, Greece

Analysis of perchlorethylene in groundwater before and after its

degradation by helical-sorbent extraction and gas chromatography

I. Ciucanu and V. Agotici

West University of Timisoara, Department of Chemistry, Romania

M. Draga and R. Barna

School of Mines, Albi, France

ABSTRACT
An integrated method of dynamic extraction of
perchlorethylene (PCE) with polydimethylsilox-
ane (PDMS) helical-sorbent followed by injec-
tion into a gas chromatograph for analysis was
developed for the determination of the real con-
centration of PCE in groundwater before and af-
ter its degradation by oxidation with KMnO4.
The main parameters (agitation, temperature,
salts, pH) that affect the extraction efficiency
have been evaluated and optimized. The in-
crease of the extracted amount of PCE due to
the presence of the salts could be partially com-
pensated by the opposite effect of the insoluble
MnO2, and of the presence of HCl and the
global effect of the matrix would be less impor-
tant for the reproducibility of the PCE extrac-
tion. The quantitative analysis of PCE was car-
ried out with the external standard method using
the calibration-curve technique. The limit of de-
tection for flame ionization detector was found
in the range 0.05-1.0 mg PCE/L of water. The
solubility of PCE in water was studied by
PDMS helical-sorbent extraction of PCE from
standard solution with different amounts of PCE
added into the same volume of water and was
found to decrease with settling time, because the
fine droplets created during the agitation of the
mixture were slowly merged in drops on the
bottle walls and were not transferred into the ex-
traction vial for GC analysis. The limit of solu-
bility was evaluated using a graphical method
and was estimated at 224.2 ± 15.7 mg PCE/L of
water at 25ºC.
1. INTRODUCTION
Volatile organic compounds (VOC's) containing
chlorine substituents such as tetrachloroethene
(PCE) and trichloroethene (TCE) have been
widely used as industrial solvents for metal
cleaning and degreasing processes, in dry clean-
ing factories, heat-exchange fluids, typewriter
correctors, plastic and fumigant manufacturing
industries (Siegrist et al., 2001). Chlorinated
solvents, known as Dense Non-Aqueous Phase
liquids (DNAPLs) are typically denser and less
viscous than water. They have different limits of
solubility in water. PCE is approximately 40
times less soluble then trichloromethane (Kue-
per et al., 2003). Unfortunately, the limit of
solubility for PCE was found in the range from
120 mg/L to 485 mg/L at 25 °C (Horvath et al.,
1999). All these organochlorinated compounds
are considered hazardous waste in many indus-
trialized countries. Intentional or accidental
leaks and spills cause contamination of ground-
water and soils. The discharge of even a small
quantity of organoclorinated compounds can
lead to long-term contamination of both the un-
saturated and saturated zones at the site. The
DNAPLs have the ability to migrate to signifi-
cant depths, in the subsurface, where they
slowly dissolve into the groundwater causing
the aqueous phase plume (Scott and Bruce,
2006).
The contamination of the water resource by
organochlorinated solvents is a matter of great
common interest worldwide because they are
classified “probably” carcinogenic to humans.
Their persistence in both biotic and abiotic envi-
ronments, their toxicity and potential carcino-
genesis have led to the considerable necessity to
3rd AMIREG International Conference (2009): Assessing the Footprint of
Resource Utilization and Hazardous Waste Management, Athens, Greece
remove these pollutants from contaminated
sites. The classical technologies (pump & treat)
capable to treat the aqueous plume are expected
to take several decades and are expensive
(Reitsma and Dai, 2000). Most popular tech-
nologies are: volatilization technologies (vapor
extraction, air sparging or stripping), thermal
technologies (steam injection, electrical heating,
vitrification), electrokinetics, bioremediation,
barriers-containment, flushing technologies (al-
cohol or co-solvent, surfactant and oxidant
flushing (In Situ Chemical Oxidation - ISCO)
(Fountain, 1998). Practically, during the reme-
diation process it is necessary to measure accu-
rately the aqueous concentrations of DNAPL
(PCE), for a range from zero to solubility limit.
Consequently, the determination of the aqueous
concentration of DNAPL with a high accuracy
is a very important task in order to confirm the
degradation of the pollutants and the moments
when the organic compounds are below suitable
level.
This paper describes experiments undertaken
to determine the suitability of the extraction
with PDMS helical solid sorbent for the moni-
toring of the PCE level in the groundwater
sources during its degradation by in situ chemi-
cal oxidation process. The limit of solubility of
the PCE in water has also been evaluated with
this technique.
2. EXPERIMENTAL
2.1 Chemicals and Materials
High-purity PCE and n-hexane were purchased
from Fisher Scientific-Labosi (Elancourt,
France). PCE is toxic and must be handled care-
fully in fume hood. Kalium permanganate
(KMnO4), kalium chloride (KCl), sodium sul-
fate (Na2SO4) and manganese dioxide (MnO2)
were from Sigma-Aldrich Chimie (ST Quentin
Fallavier, France). Deionized water was ob-
tained with a Milli-Q water purification system
(Millipore, ST Quentin En Yvelines, France)
and was held for 10 h in ultrasonic cell at 25 °C
for degassing.
The 100-µm thick non-bonded polydimethyl-
siloxane (PDMS) fibers and the manual fiber
holder were from Supelco (Bellefonte, PA,
USA).
Standard PCE aqueous solution were pre-
54
pared by adding to well known amounts of pure
PCE deionized water up to fill 255 mL glass
bottle. The mixture was magnetically stirred at
25 °C for a rapid dissolution. The agitation was
stopped after 5h and was followed by 24 h of
static equilibration. An aliquot of solution was
transferred with a syringe into the extraction
vial.
2.2 Preparation of Helical Solid Sorbent.
Details of the preparation of the helical solid
sorbent have already been described (Ciucanu,
2002). The solid sorbent used in these experi-
ments was actually a soft solid consisting of
PDMS rubber. This soft solid sorbent was
coated on a helical support made by wrapping a
wire around a straight wire with the same di-
ameter at a constant pitch. The helical support
was coated with several layers of PDMS by
immersion of the helical support in a concen-
trated solution of PDMS in dichloromethane.
PDMS cross-linking was accomplished by add-
ing 0.8 % dicumyl peroxide to the coating solu-
tion. After each coating, the solvent was evapo-
rated by heating the helical sorbent at 150 °C for
30 min. The thickness of the final coating poly-
mer depended on the concentration of PDMS
solutions and the number of coatings. The heli-
cal sorbent was weighed after each coating. The
final length of the helical sorbent was adjusted
to give the same amount of PDMS as on a 100-
μm Supelco PDMS fiber in order to compare the
amounts extracted with these solid sorbents.
2.3 Solid-Phase Extraction with PDMS Helical
Sorbent
The PDMS helical sorbent sheathed in a needle
was housed in the manual holder device. All the
extractions with PDMS fibers were performed
in 2 mL extraction vials filled with 2 mL of
PCE standard solution and involved a few sim-
ple steps (Ciucanu et al., 2004). A small mag-
netic stirring bar was added to the vial and was
tightly capped with Teflon coated silicon septa.
The extraction temperature was adjusted by the
immersion of the vial into a regulated tempera-
ture controlled water bath and let to stay for
5 min before carrying out the extraction.
2.4 Gas Chromatography
The gas chromatographic analysis of the ex-
tracted analytes was carried out on an Agilent
3rd AMIREG International Conference (2009): Assessing the Footprint of
Resource Utilization and Hazardous Waste Management, Athens, Greece
6890 N gas chromatograph with a flame ioniza-
tion detector (FID). By exposing the coating fi-
ber in the GC injector at 220 °C for 5 min, the
analytes was desorbed. The injector was operat-
ing in splitless mode. GC separation of the ana-
lytes was performed on a RTX-624 capillary
column (60 m x 0.53 i.d. and 3 µm film thick-
ness) from Restek (Lisses, France). Helium was
used as carrier gas at a constant flow of
1 mL/min. The GC oven temperature was
started at 60 °C and after 2 min was increased to
150 °C with 10 °C/min and then to 220°C with
30 °C/min. The detector temperature was main-
tained. Before sampling, the new solid sorbent
were conditioned for about 2 h in the GC injec-
tor port at 280 °C. Quantitative evaluation was
performed by the external standard calibration
method. The calibration curve was done plotting
of the GC detector signal versus five different
standard concentrations.
3. RESULTS AND DISCUSSION
3.1 Influence of the Temperature and Agitation
The extraction of PCE with PDMS solid sorbent
is an equilibrium process and the time necessary
to reach equilibrium can be estimated studying
the parameters that affect the mass transfer of
the analytes from bulk solution into the PDMS
solid sorbent. The extraction time depends for
one specific analyte and sorbent on agitation,
temperature and sample matrix.
The extraction time was measured from the
insertion of the PDMS sorbent into the sample
solution until it was retracted into the protection
needle. The time required to reach the extraction
equilibrium can be determined from the extrac-
tion curve when the steady state is reached. In
2 mL extraction vial with 200 mg PCE/L pure
water, at 5 h settling time, 500 rpm, and 25 °C,
the extraction equilibrium was reached in
25 min for Supelco PDMS fiber sorbent and
12 min with PDMS helical sorbent. A longer
extraction time did not increase the amount of
extracted PCE.
The agitation of the liquid sample improves
only the mass transport of analytes from the
bulk of the liquid phase into the sorbent layer.
In the above conditions, increasing the speed of
the magnetic stirrer up to 500 rpm, the aqueous
phase is better homogenized so that the analytes
55
present in sample have a faster access to the
helical sorbent decreasing the extraction time.
When the stirrer speed was higher than 500 rpm,
no change of the extraction time has noticed.
Increasing the sample temperature generated
a decrease of the amount of PCE extracted at the
same extraction time. For this reason, the high
temperature for extraction could be a major
concern if the sensitivity is not sufficient to
quantify PCE at ppb levels. In such cases, the
extraction at room temperature (25 °C) is indi-
cated, even if a higher temperature could im-
prove the extraction rate.
3.2 Influence of the Sample Matrix
The degradation of PCE from groundwater by
oxidation with KMnO4 can be described (Hood
et al., 2000) by the global reaction:
3C2Cl4+4KMnO4+4H2O→6CO2+4MnO2
+4KCl+8HCl [1]
The aqueous matrix will contain various re-
action products such as KCl, MnO2 and HCl.
During the oxidation process, it has not been
observed other organic products. For the kinetic
study of the oxidation process (Yan and
Schwartz, 1999), an aqueous solution of
Na2S2O3 is injected into the oxidation mixture in
order to stop the PCE degradation by the reduc-
ing of the oxidant in a fast concurrent reaction:
3Na2S2O3+8KMnO4+H2O→3K2SO4+
3Na2SO4+8MnO2+2KOH [2]
Two new salts will be generated in the sys-
tem. In the case of a solution of 180 mgPCE/mL
of water that is under the limit of solubility, the
total amount of inorganic compounds
(0.00041 g MnO2/mL; 0.00012 g KCl/mL;
0.00011 g HCl/mL; 0.00020 g K2SO4/mL;
0.00016 g Na2SO4/mL; 0.00004 g KOH/mL) is
small. Figure 1A shows the influence of the pH
on the PDMS fiber extraction of PCE from wa-
ter. The pH vas modified adding different
amounts of hydrochloric acid or potassium hy-
droxide. The amount of hydrochloric acid gen-
erated in the oxidation process might increase
the pH up to 3 and consequently will increase
the extracted amount of PCE. The influence of
the salts generated in the oxidation process on
the PDMS helical sorbent extraction is shown
Fig. 1B. An increase in the concentration of
3rd AMIREG International Conference (2009): Assessing the Footprint of
Resource Utilization and Hazardous Waste Management, Athens, Greece
Figure 1: Sample matrices effects on PCE extraction effi-
ciency: A) Influence of pH. B) Influence of salts. Condi-
tions: 2 mL extraction vial with 50 mg PCE/L pure water,
5 h settling time, 10 min extraction time, 500 rpm, and
25°C.
Na2SO4 and KCl generated an increase in the
amount of PCE extracted by sorbent. K2SO4 had
a similar effect than Na2SO4. An explanation of
these effects from Fig. 1B could be found in the
increase of the ionic strength of matrix in the
presence of the ionic species from salts, which
reduces the solubility of the neutral organic ana-
lyte in polar aqueous matrix and increase its
solubility in non-polar PDMS. The presence of
MnO2 in the matrix decreased the efficiency of
extraction. This suggests that the insoluble
MnO2 in this aqueous matrix can cover the sur-
face of the PDMS sorbent and reduces the ac-
cess of the analytes to sorbent. These influences
of the ionic species presented in the oxidation
aqueous matrix can be minimized by dilution of
sample. However, one should never forget that
the dilution of sample will automatically reduce
the sensitivity of analysis. The sample after oxi-
dation is a relatively diluted in inorganic com-
pounds and they do not have a significant influ-
ence on the extracted amount of PCE. Moreover
the increase of the extracted amount due to the
56
presence of the salts could be partially compen-
sated by the opposite effect of the insoluble
MnO2 and of the presence of HCl. Conse-
quently, the global effect of the matrix would be
less important for the reproducibility of the PCE
extraction.
3.3 Quantitative Determination of PCE in Water
The first step in quantification was the estab-
lishment of the limit of linearity of the detector
response without overloading the GC column.
The linearity of the FID was checked out by di-
rect injection of different concentrations of PCE
in n-hexane. Plot the peak area (Y) versus mg
PCE/L hexane (X) was linear (Y=375.9 X) with
a regression coefficient of R2=0.9992 up to
1000 mg PCE/L of n-hexane. The quantitative
analysis of PCE was performed with the exter-
nal-standard method using the calibration-curve
technique. The dissolution protocol consisted in
the complete filling of the bottles with water
followed by magnetic stirring at 500 rpm for
10 h at 25 °C. After this step, each series of vi-
als were maintained at 25 °C without stirring for
5 h, 30 h, 165 h, and 600 h.
3.4 Determination of the PCE Limit of Solubility
in Water
The peak area of PCE has a linear variation
function of mg PCE added in 1 L of water up to
200 mg PCE/L of water. The increase of the
amount of PCE further gave an asymptotic
variation for the corresponding peak area. The
plateau of this curve is the result of the satura-
tion and is an equilibrium process. When the
settling time was increased, the peak area values
were smaller for the same value of mg PCE/L of
water, because the fine droplets created during
the agitation of the mixture were slowly merged
in drops on the bottle walls and were not trans-
ferred into the extraction vial for GC analysis.
For the settling time higher than 600 h, the peak
area values are very closed, showing that equi-
librium was reached. Consequently, the limit of
solubility can be estimated at 600h of the set-
tling time. Plotting the amount of PCE extracted
as a function of the amount of PCE added in the
standard solutions for 600 h of settling time, we
obtained the graph from Figure 2. The limit of
solubility is determined using a graphical
method as the intersection between the tangent
to plateau of the curve from Figure 2 with the
3rd AMIREG International Conference (2009): Assessing the Footprint of
Resource Utilization and Hazardous Waste Management, Athens, Greece
Figure 2: Graphical method for the determination of the
solubility limit of PCE in deionized water. Conditions:
2 mL extraction vial, 600 h of settling time, 12 min ex-
traction time, 500 rpm and 25°C.
calibration line. We propose the limit of solubil-
ity of PCE in water at 25 °C the value of
224.2±15.67 mg PCE/L of water.
4. CONCLUSIONS
This study shows that the PDMS helical sorbent
extraction followed by GC analysis is a suitable
and reliable method for quantitative analysis of
PCE from groundwater before and after in situ
chemical oxidation of PCE with KMnO4. The
optimum extraction time was 12 min for mag-
netic stirring at 500 rpm at 25 °C. The presence
of KCl, Na2SO4 and K2SO4 increased the ex-
tracted amount of PCE. HCl and the insoluble
MnO2 have an effect in the reverse direction and
the global matrix effect on the extraction effi-
ciency can be ignored at much diluted solutions.
The flame ionization detector has a very good
linearity up to 1000 mg PCE/L of hexane. The
solubility of PCE in water depends on the set-
tling time due to the formation of very fine
droplets of PCE during the agitation of the PCE
and water mixture. The optimum settling time
was 600 h. Consequently, the limit of solubility
was estimated at 224.2±15.7 mg PCE/L of water
at 25 ºC using standard solutions with different
amounts of PCE per liter of water at a settling
time of 600 h on the base of a graphical method.
ACKNOWLEDGMENT
Financial supports for Project 2521/2009 with
CNCSIS- UEFISCSU from Romanian Ministry
of Education and Research were gratefully ac-
knowledged.
57
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