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Abstract
During oil and gas exploitation, large amounts of produced water are generated. This water has to be analyzed with relation to the chemical
composition to deduce the environmental impact of its discharge after a treatment process. Therefore, a study was carried out to evaluate preliminarily the
BTEX (benzene, toluene, ethylbenzene and xylenes), polycyclic aromatic hydrocarbons (PAHs) and metals contents in produced water samples taken
from effluents of the Bonsucesso treatment plant located in the city of Carmópolis, the most important oil and gas producer in the State of Sergipe, North-
east of Brazil. Three methods were optimized to determine the target compounds. Polycyclic aromatic hydrocarbons were determined by gas
chromatography with mass spectrometric detection (GC/MS), volatile aromatic hydrocarbons (BTEX) by gas chromatography with photoionization
detector (GC/PID) and metals were analyzed by flame atomic absorption spectrometry (FAAS). The results showed that concentrations of the target
compounds in these samples ranged from 96.7 to 1397 μg L− 1 for BTEX, from 0.9 to 10.3 μg L− 1 for PAHs and from 0.003 to 4540 mg L− 1 for metals.
© 2006 Elsevier B.V. All rights reserved.
Keywords: Purge and trap GC/PID; GC/MS; FAAS; Produced water; PAHs; BTEX; Metals
including BTEX, polycyclic aromatic hydrocarbons (PAHs), Sergipe, Brazil). For PAHs, the volumes were 1 L in amber
organic acids, phenols and alkylated phenols, metals, radio- glass bottles pretreated with acetone and methanol. For BTEX,
nuclides and a very high salt concentration. 50 mL bottles were filled to capacity to avoid any headspace.
Some studies have been described in the literature on chemical After filling with water, the bottles were sealed with Teflon-
characterization of produced water from offshore oilfield plat- lined screw caps and transported on the same day to the labo-
forms in China, Norway, Austria and the United States [5–10]. In ratory under refrigerated conditions. In the laboratory, samples
Brazil, limited monitoring has been carried out on naturally- were preserved at a temperature of 4 °C, and then diluted for
occurring compounds such as organic acids, phenols, metals, further analysis of BTEX. For metal analysis, samples were
PAHs and BTEX in produced water. Among them, there are collected in 1 L acid-washed polyethylene bottles. After filling
studies on the evaluation of different technologies for oilfield with water, the bottles were sealed with Teflon-lined screw caps
wastewater treatments from the Campos Basin, State of Rio de and transported on the same day to the laboratory under refrig-
Janeiro [11,12]. However, there is a general lack of data on the erated conditions. In the laboratory, samples were preserved at a
chemical composition of produced water from oilfields in the temperature of 4 °C before utilization.
State of Sergipe. The chemical composition of produced water is
field-dependent. So, the field-specific detailed chemical charac- 2.3. Sample preparation
terization of produced water from each oilfield or platform is
necessary in order to predict the fate and effects of the produced The samples for PAHs and BTEX analyses were not filtered.
water discharged to the environment. Before metal analysis, the samples were filtered through a
Taking into account the above considerations and considering 0.45 μm Millipore filter. Determination of ammonia was made
that, to date, no data on chemical composition of the oilfield using the indophenol blue reaction, while the azide-Winkler
produced water in the State of Sergipe have been reported in the method and electrical conductivity were used to measure dis-
literature, this paper provides a preliminary evaluation of the levels solved oxygen and salinity, respectively.
of BTEX, PAHs and metals in the effluent of produced water from
the Bonsucesso treatment plant located in the city of Carmopólis, 2.4. Apparatus
State of Sergipe. This treatment station receives produced water
from a number of different petroleum production units. 2.4.1. Purge and trap conditions
A Tekmar–Dohrmann velocity XPT purge-and-trap (Mason,
2. Experimental Ohio, USA) was used to pre-concentrate the BTEX in produced
water. The P and T unit consists of a 5 mL stripping vessel. No
2.1. Chemicals and materials cryogen was needed for BTEX trapping, using Tenax TA as
adsorbent trap. The water sample was purged with helium
Dichloromethane, acetonitrile and n-hexane were nanograde (99.995% purity) at 40 mL min− 1 during 11 min at 26 °C. The
(Mallinckrodt Baker, Paris, KY, USA). Certified standards of volatiles were thermally desorbed (180 °C, 4 min), and transferred
BTEX (benzene, toluene, ethylbenzene and m-xylene, o-xylene to the GC/PID-FID via a transfer line heated to 100 °C. After
and p-xylene) were purchased from ChemService at concentra- desorption, the trap was cleaned by heating at 200 °C for 8 min.
tion of 2000 μg mL− 1 in methanol (West Chest, PA, USA).
Intermediate solutions were prepared by diluting the standard 2.4.2. GC/PID-FID conditions
mixture at concentrations of 5 and 50 μg mL− 1 in methanol. The A Shimadzu 17A gas chromatograph (Kyoto, Japan) equipped
deionized water used for preparing working solutions was puri- with photoionization (PID) and flame ionization (FID) detectors
fied by a Millipore (Bedford, MA, USA) Milli-Q water purifica- and a split/splitless injector was used for quantification of BTEX.
tion system. Certified standards of the 12 PAHs were purchased A fused-silica megabore column, DB-624 (6% cyanopropyl-
from AccuStandard (New Haven, CT, USA): naphthalene, phenyl–94% dimethylpolysiloxane; 75 m × 0.53 mm I.D.,
acenaphthene, phenanthrene, anthracene, fluoranthene, pyrene, 3 μm), supplied by J and W Scientific (Folsom, CA, USA),
benzo[a]anthracene, chrysene, benzo[a] pyrene, perylene, benzo was employed, with helium (purity 99.995%) as carrier gas at a
[e] pyrene, benzo[g,h,i] perylene. The stock solutions of the PAH flow-rate of 10 mL min− 1 . The column temperature was
were prepared in acetonitrile at 100 μg mL− 1 and stored at programmed as follows: 30 °C for 1 min, increasing to 100 °C
−18 °C. The working standard solutions were prepared by diluting at 5 °C min− 1 and directly to 220 °C at 8 °C min− 1 then holding for
the stock solutions in dichloromethane as required. All standards 5 min. The injection port and detector were operated at 180 and
were at least 99% pure. All stock solutions of metals (1000 μg 220 °C, respectively. The PID system was operated with a 10 eV
mL− 1) were stored in nitric acid-washed polyethylene bottles. bulb and at an intensity of 1 mA.
Analytical grade anhydrous sodium sulfate and silica-gel 60 (70–
230 mesh) were supplied from Merck (Darmstadt, Germany). 2.4.3. Flame atomic absorption spectrometric conditions
A Shimadzu (Kyoto, Japan) AA-6800 flame atomic
2.2. Sampling absorption spectrophotometer equipped with BCG-D2 back-
ground correction was used for determining the metals. The
Produced water samples were collected from the Bonsucesso instrumental adjustments were determined according to the
treatment station located in the city of Carmópolis (State of recommendations of the manufacturer.
236 H.S. Dórea et al. / Microchemical Journal 85 (2007) 234–238
2.4.4. GC/MS conditions high percentage of the total amount of produced water dis-
A Shimadzu system consisting of a QP-5050A mass spec- charged into subsurface waters from the oilfields of the State
trometer equipped with a GC-17A gas chromatograph with a of Sergipe.
split/splitless injector was used for the quantification and
confirmation of the polycyclic aromatic hydrocarbons. A fused- 3.2. BTEX analysis
silica column, DB-5 ms (5% phenyl-95% dimethylpolysilox-
ane; 30 m × 0.25 mm I.D., 0.25 μm), supplied by J and W The above described extraction procedure was developed on
Scientific (Folsom, CA, USA), was employed with helium the basis of EPA method 524.2 (purgeable organic compounds
(purity 99.995%) as carrier gas at flow-rate of 1.5 mL min- 1. by the PT technique) [14]. To find the extraction conditions
The column temperature was programmed as follows: 40 °C for providing the highest yields of BTEX from the produced water
1 min, increasing to 160 °C at 25 °C min- 1 and directly to and to validate the method for the simultaneous determination
300 °C at 5 °C min- 1 and holding for 6 min. The solvent delay of these analytes, some parameters of the purge and trap system
was 5 min. The injector port was maintained at 250 °C and 1 μL and of the chromatograph were optimized: Purge and desorption
volume was injected in splitless mode (1.0 min). The data were times and temperatures; transfer line and column temperatures;
acquired and processed by the Shimadzu Class 5000 software. detector selection (PID or FID). The m-and p-xylenes were not
The effluent from the GC column was transferred via a transfer separated and were determined together.
line held at 280 °C and fed into a 70 eV electron impact After the definition of the analytical conditions for the PT-
ionization source held at 280 °C. The analysis was performed in GC/PID-FID, a study of comparison was performed between the
the selected ion monitoring (SIM) mode. two gas chromatographic detection systems (PID and FID) to
find the detector providing the highest sensitivity using standard
2.5. Methods solutions at 4 ng mL− 1. Considering the results, PID showed
higher sensitivity ranging from 5.6 (for the ethylbenzene) to 7.2
2.5.1. Procedure for BTEX analysis (for the m + p-xylenes) times greater than FID. Hence, PID was
An analytical aliquot of 5 mL of produced water with 10 μL chosen for determining BTEX in produced water.
of α, α, α-trifluorotoluene (surrogate) was transferred to the P Recovery assays were done in triplicate by spiking produced
and T port without air bubbles. The sample was purged with water samples at two levels (4 and 40 μg L− 1). The mean
helium and the volatiles were trapped on the Tenax adsorbent recoveries obtained with spiked samples at the 4 μg L− 1 level
and thermally desorbed into the GC/PID system. ranged from 105.5% to 138.6%, with relative standard devia-
tions (RSD) between 10% and 19.8%, while at 40 μg L− 1
2.5.2. Procedure for polycyclic aromatic hydrocarbon analysis recoveries ranged from 99.9% to 104.3%, with RSD between
An analytical aliquot of 1000 mL of produced water sample 1.2% and 3.5%. Surrogate standard was added to each extraction
was placed in a separating funnel. 30 mL of n-hexane were to control any losses during the analysis procedures. Addition-
added and the mixture was extracted for 20 min in a manual ally, each analytical sequence included quality control standards
shaker. The residue was re-extracted with another 2 × 30 mL of and blanks to check noise and background levels, possible
n-hexane. The extract was concentrated using a rotary carryover effects and to cover small retention time variations.
evaporator (35 °C) and was transferred to at chromatographic Six point (average of three injections) calibrations (based on
column filled with 0.5 g of silica-gel (200–325 mesh) and 5 g of peak areas) were obtained over the concentration range of
anhydrous sodium sulfate. The PAHs were eluted with 20 mL of interest (2–200 μg L− 1 for m + p-xylenes and 1–100 ng mL− 1
n-hexane:dichloromethane (70:30, v/v) mixture and evaporated for other species). Calibration curve correlation coefficients
to nearly 0.1 mL under a gentle stream of nitrogen. The residue were higher than 0.9998 in all cases. The analytical calibration
was dissolved in dichloromethane (1 mL) and an aliquot (1 μL) curves were used for quantification purposes using the external
was analyzed by GC/MS. standards procedure. The limits of detection (LODs) were verified
by analyzing the BTEX mixture at 0.5 μg L− 1. LODs ranged from
2.5.3. Procedure for heavy metal analysis 0.06 μg L− 1 for xylenes to 0.12 μg L− 1 for benzene, while the
After the metals had been extracted from the matrix using the limits of quantification (LOQs) ranged from 0.21 μg L− 1 for
ammonium pyrrolidine dithiocarbamate (APDC) in methyl xylenes to 0.41 μg L− 1 for benzene.
isobutyl ketone (MIBK) method [13], the metals were measured
in the organic phase by FAAS. 3.3. Polycyclic aromatic hydrocarbon analysis
3. Results and discussion The liquid–liquid extraction procedure described above was
developed on the basis of the EPA 3510 and 8270C methods
3.1. General comments [15,16] and the Reddy and Quinn procedure [17]. The pro-
cedures given in these sources were modified and further im-
This study reports on results obtained from a survey of proved for produced water analysis. Positive identification of
wastewater from the Bonsucesso produced water treatment the total PAHs was achieved first by mass spectral identification
plant for the levels of BTEX, PAHs and metals in the effluent. and then by acquisition of standard PAHs and comparison with
This treatment plant was selected because it contributes a unknown GC retention times.
H.S. Dórea et al. / Microchemical Journal 85 (2007) 234–238 237