Effectiveness of Air Stripping, Advanced Oxidation, and

Activated Carbon Adsorption-Coupled Process in Treating

Chlorinated Solvent–Contaminated Groundwater
Bingzhi Li1; Kuangfei Lin2; Wei Zhang3; Shuguang Lu2; and Yongdi Liu4
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Abstract: Chlorinated solvents are the most prevalent organic contaminants in groundwater because of their extensive and widespread use as
cleaning agents and metal degreasers, and they have become a significant threat to groundwater supplies. Groundwater contamination by
chlorinated solvents has proven difficult and costly to remedy because of the physicochemical properties of the solvents. This study was
conducted to examine the effectiveness of treating contaminated groundwater containing chlorinated solvents using air stripping, advanced
oxidation, and activated carbon adsorption processes. The results showed that the stripping instrument could effectively transfer chlorinated
solvents into the gas phase within several minutes at an airflow rate of 5.0 L= min and a temperature of 298 K. The residual chlorinated
solvents were further oxidized into harmless by-products by the subsequent O3 =H2 O2 process, and the off-gas generated from the previously-
mentioned processes were collected and absorbed by four types of activated carbon [i.e., Shanghai coconut, Shanghai fruit, Taixi coal
(12
40) and Taixi ZJ-15 (cylinder)]. Shanghai coconut exhibited the greatest adsorption capacity, at 0.5 g=g. Two types of contaminated
groundwater containing chlorinated solvents from contaminated sites were successfully treated by the coupled process at bench scale with the
effluent concentrations of chlorinated solvents complying with the target values standard for groundwater regulated by the Dutch Ministry of
Public Housing. Overall, the study found that the proposed coupled process is a viable method for efficiently and effectively remediating
shallow contaminated groundwater containing chlorinated solvents in southern China. DOI: 10.1061/(ASCE)EE.1943-7870.0000557.
© 2012 American Society of Civil Engineers.
CE Database subject headings: Groundwater pollution; Solvents; Chlorine; Adsorption.
Author keywords: Effectiveness; Chlorinated solvent; Contaminated groundwater; Coupled process.

Introduction industrial activities in recent decades, a large number of ground-

Groundwater is an important water source in many countries. The
National Groundwater Association in the United States (NGWA
2009) estimates that 75, 44, 32, 29, and 15% of the populations
of Europe, the U.S., the Asian-Pacific region, Latin America,
and Australia, respectively, depend on groundwater for their drink-
ing water supply. Unfortunately, because of a diverse range of
1
Postdoctorate, State Environmental Protection Key Laboratory of
Environmental Risk Assessment and Control on Chemical Process, East
China Univ. of Science and Technology, P.O. Box 563, Number 130,
Meilong Road, Shanghai 200237, China (corresponding author). E-mail:
libingzhi2008@yahoo.cn
2
Professor, State Environmental Protection Key Laboratory of Environ-
mental Risk Assessment and Control on Chemical Process, East China
Univ. of Science and Technology, P.O. Box 563, Number 130, Meilong
Road, Shanghai 200237, China.
3
Associate Professor, State Environmental Protection Key Laboratory
of Environmental Risk Assessment and Control on Chemical Process,
East China Univ. of Science and Technology, P.O. Box 563, Number
130, Meilong Road, Shanghai 200237, China.
4
Professor, State Environmental Protection Key Laboratory of Environ-
mental Risk Assessment and Control on Chemical Process, East China
Univ. of Science and Technology, P.O. Box 377, Number 130, Meilong
Road, Shanghai 200237, China.
Note. This manuscript was submitted on November 21, 2011; approved
on February 22, 2012; published online on February 23, 2012. Discussion
period open until February 1, 2013; separate discussions must be submitted
for individual papers. This paper is part of the Journal of Environmental
Engineering, Vol. 138, No. 9, September 1, 2012. © ASCE, ISSN 0733-
9372/2012/9-903-914/$25.00.
water sites have been contaminated with artificial chemicals,
and this has become a worldwide problem (Futagami et al.
2008). Chlorinated solvents are by far the most prevalent organic
contaminants in groundwater because of their extensive and wide-
spread use as cleaning agents and metal degreasers (Stroo et al.
2003). For example, chlorinated aliphatic hydrocarbons (CAHs),
such as trichloroethylene and perchloroethylene, are found at ap-
proximately 80% of all Superfund sites with groundwater contami-
nation and at more than 3,000 Department of Defense (DoD) sites
in the United States (U.S. EPA 1997). In contrast to the situation in
the United States, urban groundwater pollution in China is becom-
ing an increasingly acute problem. According to continuous mon-
itoring data of 118 cities over periods of 2–7 years, approximately
64% of urban areas in China suffered serious groundwater pollu-
tion, 33% were lightly polluted, and only 3% were considered free
of contamination (Hao 2004). Although no detailed public report
on the current state of groundwater pollution by chlorinated sol-
vents in China is available, some surface water and groundwater
in Hangzhou, Shenyang, and Taihu Lake basin areas, for example,
have been found to be polluted to varying degrees by chlorinated
solvents (Yu et al. 2007; Lu et al. 2009; Chen et al. 2005; Liu et al.
2005). Furthermore, with rapid development and urbanization
underway in China, a great many enterprises from heavily-polluted
industries have been closed or relocated to suburban districts. It is
estimated that several thousands of enterprises in Beijing, Jiangsu,
Liaoning, Guangdong, Chongqing, and other cities have been in-
volved in the process, and approximately 300,000 acres of indus-
trial lands had been replaced by 2008 (China Ministry of
Environmental Protection 2010). An increasing number of newly

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J. Environ. Eng. 2012.138:903-914.

 contaminated groundwater supplies are being found in which high
concentrations of multi-component organic materials are present,
including volatile chlorinated solvents and non-volatile toxic per-
sistent organic pollutants (POPs), posing a great threat to ground-
water resources in China. In recent years, Chinese government
funding has helped to develop remediation technologies and equip-
ment for selected types of contaminated sites. Although various
groundwater remediation technologies exist, only a few are both
practically and economically feasible (World Bank Report
2010). Consequently, there is an urgent need to develop quick
and cost-effective remediation techniques for the redevelopment
of contaminated groundwater supplies in China.
Effective treatment methods commonly employed for the re-
moval of chlorinated solvents from contaminated waters and
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groundwater include air stripping (Reddy et al. 1995; Murray et al.
2000; Adams et al. 2011), granular activated carbon adsorption
(Giffin et al. 1998; Yue et al. 2001), and biodegradation (Kao
et al. 2000; Cunningham et al. 2001; Tiehm et al. 2011). Phytor-
emediation, the treatment of contaminated water or soil with plants,
has also been evaluated as another treatment method for chlorinated
solvents (Ma et al. 2009; James et al. 2009). These treatment tech-
niques have some inherent disadvantages. For example, in air strip-
ping and granular activated carbon adsorption, the volatile
components are transferred from the water into another phase that
needs further treatment before final disposal. The slower degrada-
tion rate associated with biodegradation limits large-scale applica-
tion, and high concentrations of chlorinated solvents could have
adverse effects on the microorganisms in the biodegradation media,
resulting in a reduction in the efficiency of contaminant removal by
this method (Teerkum et al. 2007). Therefore, alternative treatment
methods need to be developed for the removal of volatile and
non-volatile components present in contaminated groundwater. Ad-
vanced oxidation processes (AOPs), which involve the application
of various combinations of O3 , H2 O2 , ultraviolet (UV), and semi-
conductors, provide promising treatment options. The major advan-
tage of AOPs is attributed to the hydroxyl radical (HO•) that
indiscriminately attacks almost any organic compound with a very
high reaction rate constant. Moreover, HO• oxidizes a wide variety
of organic pollutants into innocuous intermediate and end products,
as opposed to conventional treatment methods by which pollutants
are transferred from one medium to another. In summary, it is
difficult to achieve satisfactory results by relying solely on one type
of process; thus, development of coupled processes is imperative.
To this end, the objectives of the present study were the follow-
ing: (1) investigate the feasibility of treating contaminated ground-
water containing volatile chlorinated solvents by individual air
stripping, advanced oxidation and granular carbon adsorption proc-
esses, and (2) propose a coupled process and verify its effectiveness
in treating two types of contaminated groundwater from typical
contaminated areas, thereby establishing theoretical foundations
and guidelines for practice for the remediation of shallow ground-
water contaminated by volatile and/or non-volatile organic contam-
inants in the southern region of China.
Materials and Methods
Materials
Hexane(C6 H14 ,97%),trichloroethene(TCE,99%),1,1-dichloroethane
(DCA, ≥99.7%), 1,1-dichloroethene (DCE, 99.7%), cis-1,
2-dichloroethene (cis-DCE, 99.0%), 2-chloropehnol (2-CP, 99.8%),
1,1,1-trichloroethane (TCA, 98%) and tetrachloroethene (PCE,
98%) were purchased from Shanghai Jingchun Reagent Co. Ltd.
(Shanghai, China). Gas sampling bags with fluoropolymer liners
904 / JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / SEPTEMBER 2012
J. Environ. Eng. 2012.138:903-914.
were purchased from Elor Trade Co. Ltd. (Shanghai, China). Four
Chinese activated carbons–two coal carbons, a fruit nut (apricot
nut and walnut shell) carbon and a coconut shell carbon–were used
in this study. Table 1 summarizes their adsorptive capacities as
represented by their phenol, iodine, methylene blue and tannic
acid numbers. The granular activated carbon (GAC) samples were
pulverized, sieved to the desired mesh size fractions, washed with
deionized water, dried for 12 h at 105°C, and stored in glass jars. All
other reagents were analytical grade or higher. All glassware was
soaked in chromic acid, and then rinsed with tap water and distilled
water prior to use.
Ultra-pure water from a Milli-Q water process (Classic DI,
ELGA, UK) was used to prepare aqueous solutions. Four types of
GAC, namely, coconut AC (C1), fruit shell AC (C2), coal AC (C3),
and coal bar AC (C4), were selected for testing the adsorption
performance of gas-phase chlorinated hydrocarbons. Contaminated
groundwater samples from two contaminated sites in Pudong and
Jiading, both in Shanghai, were collected from a layer approxi-
mately 3–6 m deep and the upper layer of dense nonaqueous-phase
liquids (DNAPL) in the free phase below the ground surface, and
filtered using fiber filters (0.45 μm, Waters Corporation, Shanghai,
China) before the experiments. The groundwater characteristics
of the polluted sites in Pudong and Jiading are shown in Table 2
and Table 3, respectively.
Experimental Procedures
Air Stripping
The packed tower used for air stripping was 8 cm in diameter with a
working volume of 8 L and contained 50 cm of 10-cm stainless
corrugated gauze packing (Cixi Huangsheng Chemical Packing
Co. Ltd., Zhejiang, China). The tower was composed of three parts:
videlicet, air inlet and distribution section, main column and outlet
conical cap. The cap was made of stainless steel, whereas the other
parts were made of polymethyl methacrylate (PMMA). There were
four uniformly-distributed cylindrical microporous diffusers 3.2 cm
in diameter with a pore diameter of 10 μm (Shijiazhuang Beot In-
organic Membrane Separation Equipment Engineering Co. Ltd.,
Hebei, China) at the bottom, through which high-speed airflow
could be effectively controlled and diffused into tiny air microbub-
bles while a partial vacuum was created. The middle, primary, col-
umn was filled with five blocks of stainless corrugated gauze
packing lined with corrugated stainless steel screens with inclina-
tions of 30 or 50 degrees and adjacent pieces in opposite directions.
When loaded, they were staggered 90 degrees and stacked up. The
Table 1. Adsorption Capacity Indicators of the GAC Samples
Phenol Iodine Methylene Tannic
Blue Acid
GAC sample Numbera Numberb numberc numberd
Shanghai coconut 131.0 999 164 13.2
Shanghai fruit 113.0 1012 292 61.4
Taixi ZJ-15, cylinder 76.3 933 256 14.9
Taixi coal, 12
40 65.1 991 299 13.0
a
mg of phenol adsorbed by 1 g of carbon at an equilibrium phenol
concentration of 20 mg=L.
b
mg of iodine adsorbed by 1 g of carbon at an equilibrium iodine
concentration of 0.02 N.
c
mg of MB adsorbed by 1 g of carbon at an equilibrium MB concentra-
tion of 1 mg=L.
d
mg of tannic acid adsorbed by 1 g of carbon at an equilibrium tannic
acid concentration of 2 mg=L.
 Table 2. Groundwater Quality Parameters for the Pudong Site
Parameters Underground approx 3 m (I) Underground approx 6 m (II) Upper layer of DNAPL free phase (III)
pH 6.70 6.33 6.20
Temperature (°C) 26.3 26.4 26.8
Conductivity (μs=cm) 421 503 1096
TCA (mg=L) 298.27–340.41 313.68–327.33 1,251.42–1,371.04
Total organic carbon 53.84 — —
(TOC, mg=L)
Inorganic carbon (IC, mg=L) 114.30 — —
Cations Total Al (mg=kg) 4.8 4.4 4.0
Total Ca (mg=kg) 220.0 430.0 580.0
Total Fe (mg=kg) 3.1 34.0 1,100
Total K (mg=kg) 30.0 37.0 170.0
Total Mg (mg=kg) 180.0 210.0 440.0
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Total Na (mg=kg) 520.0 220.0 520.0

Total Mn (mg=kg) 1.5 3.2 7.2
Total Si (mg=kg) 3.0 14.0 12.0
Anions Cl− ðmg=LÞ 1,334.9 1,257.0 4,131.8
NO−3 ðmg=LÞ ND ND ND
SO2−
4 ðmg=LÞ 78.6 ND 418.4

Table 3. Primary Pollutants Present in Groundwater at the Jiading Site
Sampling well number
Pollutants NMW-1 NMW-5 MW-1 NMW-6
cis-DCE (μg=L) 940.0 265.0 9,270 837.0
TCE (μg=L) 118.0 55.1 3,530 18.2
PCE (μg=L) 2,130 392.2 178,000 672.0
2-CP (μg=L) 83.0 55.0 21,600 — The ozonation reaction was terminated using sodium thiosulfate.
upper section of the tower was equipped with an outlet backcone-
shaped cap with a maximum diameter three times that of the
primary column and with a volume half that of the primary column,
by which large quantities of foam generated in the air stripping
process could be effectively prevented from entering into the
off-gas collection processor with the air current.
Preliminary tests demonstrated that the temperature did not
change during the air stripping experiment (data not shown), so the
temperature-control bath was not used. For the air stripping experi-
ments, 6 L of a solution of chlorinated solvents were pumped
into the reactor by a peristaltic pump (BT300-2J, Baoding Longer
Precision Pump Co., Ltd., Hebei, China), and then air was intro-
duced into the tower from the bottom at different airflow rates.
Water and outlet gas samples were withdrawn and collected from
the middle and top of the tower at regular intervals to analyze the
concentrations of chlorinated solvents.
O3 =H2 O2 Advanced Oxidation
The airtight polymethyl methacrylate bubble column was 8 cm in
internal diameter with an effective volume of 8.0 L. The ozonation
experiment was operated in a semi-batch mode. The contaminated
groundwater was pumped into the reactor, and the ozone-containing
gas was allowed to flow upward continuously. Ozone was generated
from pure oxygen using a CFY-6 model ozone generator (Rongxin
Electronic Co. Ltd., Zhejiang, China) with a maximum capacity of
100 mg O3 · min−1 operated at 25°C and 1 atm pressure. The O3 =O2
mixture was fed into the reactor through a porous titanium plate
diffuser (10 μm) located 1 cm from the bottom of the column. The
ozone concentration was regulated by varying the oxygen flow-rate,
which was monitored by a gas flow meter. The excessive ozone in the
outlet was destroyed as it flowed through 5% KI absorption bottles.
The bubble column was pre-ozonated for 4 min to satisfy any
ozone demand in the column before experimental operation, and
then was washed several times with twice-distilled water to exclude
possible experimental interference. During the ozonation experi-
ments, the ozone flow rate was preset at 60 L=h. For the
O3 =H2 O2 system, certain quantities of H2 O2 were added before
ozonation. The ozonation time was controlled within 1 h for each
batch experiment. The ozonated effluent was sampled for further
analysis of color, major pollutants and intermediate products.
Granular Activated Carbon Adsorption
The effluent chlorinated solvent gas was connected to a GAC
column that was designed with two ports, for inlet and outlet gas
flows, respectively. The column contained almost 12 g GAC used
to absorb chlorinated solvents in the exhaust gas. Due to the high
adsorptive capacity of GAC for chlorinated solvents, the column
breakthrough experiments employed the efficient microcolumn
rapid breakthrough (MCRB) method to obtain chlorinated solvent
breakthrough curves in a small fraction of the time that would have
been necessary using the conventional test method (Chang et al.
2007). A given amount of GAC was weighed and loaded into the
column, and flow rates for mixed-gas were fixed at 2.0, 3.0, and
5.0 L= min, respectively. The adsorption was conducted under
ambient conditions, and chlorinated solvent concentrations were
adjusted by controlling the flow rates of pure chlorinated solvent
gas-phase adsorbate and air. The inlet line was switched over to
the gas mixture, and the mass change of the sample was recorded
as a function of time until an equilibrium state was reached. The
off-gas was collected for further analysis of chlorinated solvent
concentrations. This equilibration time was dependent on the flows
of mixed-gas and the adsorption characteristics of the GAC. The
adsorption capacity of each type of GAC was calculated by graphical
integration of the area above the breakthrough curve.
Analytical Methods
For analyses of aqueous samples of chlorinated solvents, a 1 mL
sample solution was required for 1 mL hexane extraction on a vor-
tex mixer for 3 min and rest for 5 min. Chlorinated solvents were
analyzed with a gas chromatograph (GC, Agilent 7890A, USA)
equipped with an electron capture detector (ECD), an autosampler
(Agilent 7693), and an HP-5 column (30 m length, 320 μm inner
diameter, 0.25 μm thickness). The temperatures of the injector
and detector were 240 and 260°C, respectively, and the oven

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J. Environ. Eng. 2012.138:903-914.

 temperature was isothermal at 60°C. The sample injection quantity
was 1 μL with a split ratio of 50∶1.
Gas samples were analyzed with a GC (Techcomp 7900,
Wuhan, China) equipped with a flame ionization detector (FID),
a six-way valve box, and a TM-5 column (30 m length, 320 μm
inner diameter, 0.5 μm thickness). The temperatures of the injector
and detector were 120 and 220°C, respectively, and the oven
temperature was isothermal at 80°C. The sample injection quantity
was 1 mL.
Intermediates formed during the chlorinated solvent oxidation
process were identified by a gas chromatography-mass spectrom-
etry device (GC/MS, Shimadzu GC/MS-QP 2010, Japan) equipped
with a DB-5 MS column (30 m length, 250 μm inner diameter,
0.25 μm thickness) using a headspace sampling procedure. The
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temperature of the injection port was 200°C and the oven temper-
ature was isothermal at 40°C. The ion source and interface tem-
peratures were 250 and 200°C, respectively. The mass ranged from
40–350 amu. The concentration of 2-CP was calculated using
a high-pressure liquid chromatography (HPLC) (Shimadzu LC-
2010HT, Japan) device equipped with a UV detector set at a
maximum absorption wavelength of 280 nm. A 4.6 × 250 mm
XDB-C18 column was used with its corresponding guard column
(Agilent, US). The mobile phase was a mixture of methanol and
water (80∶20, v=v) with a flow-rate of 1.0 mL · min−1 .
The metal content in the groundwater samples was determined
by inductively-coupled plasma (ICP) analysis using an Iris Intrepid
spectrometer (Thermo Elemental, US). An Ethos 1600 microwave
lab station (Milestone) was used to prepare an acid solution of
all samples for ICP analysis. The anions were analyzed by an
ion chromatograph (Dionex ICS-1000, US). Total organic carbon
(TOC) was determined by a TOC analyzer (Elementar Liquid
TOC, Germany). Ultraviolet-visible absorption spectra were re-
corded using a Shimadzu UV-2401PC spectrophotometer in the
range 200–600 nm. pH was measured by a pH meter (Mettler-
Toledo DELTA 320, Switzerland).
Results and Discussion
Air Stripping
Single Contaminant Stripping
For the tests described in this section, four types of chlorinated
solvents, namely DCA, DCE, TCE and TCA, were selected as
target pollutants. Their specific physical properties are shown in
Table 4.
TCE Air Stripping
Preliminary studies of air stripping were performed to test the
removal of TCE under a large air capacity of 50 L= min, a tem-
perature range of 293–313 K and TCE concentrations of
Table 4. Selected Physical Properties of Some Chemicals in This Study
Molecular Boiling point Melting point
Chemicals CAS weight (deg C) (deg C)
2-CP 95-57-8 128.56 175
DCA 75-34-3 98.96 56
DCE 75-35-4 96.94 37
cis-DCE 156-60-5 96.94 47
PCE 127-18-4 165.8 121
TCA 71-55-6 133.4 74
TCE 79-01-6 131.4 87
Source: Cohen and Mercer 1993; Montgomery and Welkom 1990.
906 / JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / SEPTEMBER 2012
J. Environ. Eng. 2012.138:903-914.
78.6–740 mg=L. The results showed that removal efficiency
reached over 90% within 5 min and that the effect of temperature
on the efficiency of TCE removal was not significant. Therefore,
room temperature, 298 K, was adopted in later experiments. When
initial concentrations of TCE were varied within the ranges 78.6–
167.6 and 302.0–740.0 mg=L, after air stripping for 5 min, residual
concentrations of TCE in the aqueous phase were within the ranges
0.82–1.06 and 9.6–17.6 mg=L, respectively, and the corresponding
TCE removal efficiencies attained were over 99% and 96.8–97.6%,
respectively. The trends were almost identical at different temper-
atures and initial concentrations: the TCE concentration decreased
rapidly in the first few minutes, and then the rate of TCE removal
decreased and reached a plateau. Further extending stripping time
did little to affect TCE removal.
In the interest of ensuring TCE removal efficiency and reducing
operational cost, airflow rates of 1.5–5.0 L= min were examined.
The results are shown in Fig. 1.
As Fig. 1 shows, the effectiveness of air stripping on TCE
removal was positively correlated with airflow rate. After 3 min
of air stripping, the residual TCE concentration ranged from
0.5–1.2 mg=L, and removal efficiency exceeded 96%. Relative
to large-capacity air stripping, smaller capacities in the range
1.5–5.0 L= min yielded better results at lower cost. For a given
air flow-rate, TCE stripping curves were independent of initial con-
centrations and divided into two stages, the first of which was a
quick-drop stage in the initial 2 min, and the second was a slow-
decline stage. Controlling stripping time within the first stage was
concluded to be more cost-effective. In subsequent experiments, a
temperature 298 K and an airflow rate of 5.0 L= min were used.
Factors that influence the cost of air stripping include pollutant
concentration, water spray density, and gas-liquid ratio. For a given
chlorinated hydrocarbon concentration and airflow rate, the
gas-liquid ratio was positively correlated with stripping time. A con-
tinuous air stripping experiment was performed to investigate TCE
limit concentration and ascertain proper stripping time for an
initial TCE concentration of 1; 000 mg=L, a temperature of 298 K
and an air flow-rate of 5.0 L= min. The results are presented in Fig. 2.
Fig. 2 shows that after 2 min of air stripping, TCE concentration
rapidly dropped from 1,000 to 1.32 mg=L and then decreased
slowly. For TCE concentrations of 1,000 and 100 μg=L, there is
still down-concentration space in spite of slower rate constants
(0.78 and 0.73 min−1 ) than in the case with a high initial concen-
tration (3.29 min−1 ). Residual TCE concentrations in the aqueous
phase were 137.9 and 21.6 μg=L at 30 and 60 min, respectively.
These concentrations meet or exceed the environment target value
for groundwater remediation for TCE set by the Dutch Ministry of
Public Housing (Table 5).
TCA Air Stripping
TCA stripping experiments were performed at a temperature of
298 K, initial TCA concentrations of 20–1; 300 mg=L and airflow
Aqueous solubility Vapor pressure Henry’s law constant
(mg=L) (mm Hg) (atm-m3 =mol)
9 2.85E þ 04 1.42E þ 00 8.28E − 06
−97 5.50E þ 03 1.82E þ 02 4.30E − 03
−122 4.00E þ 02 4.95E þ 02 2.10E − 04
−50 6.00E þ 02 2.65E þ 02 3.84E − 01
−19 1.50E þ 02 1.40E þ 01 1.53E − 02
−30 1.36E þ 03 1.00E þ 02 1.80E − 02
−73 1.10E þ 03 5.78E þ 01 9.10E − 03
 800 5.0 L/min 400 5.0 L/min

TCE concentration (mg/L)

TCE concentration (mg/L)
3.0 L/min 3.0 L/min
2.5 L/min 2.5 L/min
600 1.5 L/min 300 1.5 L/min

400 200

200 100

0 0
0 5 10 15 20 0 5 10 15 20
Time (min) Time (min)
160
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160
140 5.0 L/min 140 5.0 L/min

TCE concentration (mg/L)

TCE concentration (mg/L)

3.0 L/min 3.0 L/min

120 120 2.5 L/min
2.5 L/min
1.5 L/min 100 1.5 L/min
100
80 80

60 60

40 40

20 20

0 0
0 5 10 15 20 0 5 10 15 20
Time (min) Time (min)

Fig. 1. TCE removal by air stripping at different initial concentrations and airflow rates

1000 Table 5. Target and Intervention Values for Groundwater Containing

C0 = 1000 mg/L Chlorinated Hydrocarbons (Dutch Ministry of Public Housing)
1000
Residual TCE concentration (mg/L)

C0=1000µg/L Groundwater (μg=L in solution)

Residual TCE concentration ( µg/L)

800 900
C0=100 µg/L
800 Chlorinated hydrocarbons Target value Intervention value
700 2-CP 0.2 30
600 600 DCA 7 900
500 DCE 0.01 10
400 cis-DCE 0.01 20
400 300
PCE 0.01 40
TCA 0.01 300
200
TCE 24 500
100
200
0
0 5 10 15 20 25 30
Time (min) initial TCA concentration. For example, for an initial TCA con-
0 centration of 20 mg=L, pseudo-first-order reaction rate constants
0 5 10 15 20 increased from 0.0028–0.0167 min−1 with an increase in temper-
Time (min) ature from 298–353 K. In contrast, for a stripping temperature of
Fig. 2. TCE removal by air stripping at 298 K and an airflow rate of 298 K, pseudo-first-order reaction rate constants decreased from
5.0 L= min 0.0028–0.0011 min−1 with an increase in initial TCA concentration
from 20–1,300 mg=L. The effect of temperature on the effective-
ness of TCA stripping is concluded to be greater than that of
initial TCA concentration. However, the consequences of increas-
rate of 1.5 L= min. The stripping curves were similar to those for ing stripping temperature are greater energy consumption and
TCE shown in Fig. 2. For a given initial TCA concentration, higher operating costs. Consequently, the necessity of increasing
TCA stripping effectiveness was positively correlated with temper- stripping temperature needs to be reconsidered.
ature in the range of 298–353 K and negatively correlated with TCA
initial concentration in the range of 20–1; 300 mg=L. Further analy- DCE Air Stripping
sis revealed that TCA removal followed a pseudo-first-order reaction Fig. 3(b) shows the results of tests of DCE removal by air stripping at
kinetic model (R2 > 0.95). A 3D-color fill surface [Fig. 3(a)] was a temperature of 298 K and an airflow rate of 5.0 L= min. Quick
obtained by plotting pseudo-first-order reaction rate constants DCE removal was observed at room temperature. Residual DCE
versus stripping temperature and TCA initial concentration. concentrations in the aqueous phase at 1, 1 and 30 min of air
Fig. 3(a) indicates that the effectiveness of TCA stripping in- stripping were all lower than 1 mg=L and the corresponding removal
creases with increasing temperature and decreases with increasing efficiencies attained were 99.3, 99.6 and 99.9% for DCE

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J. Environ. Eng. 2012.138:903-914.

 Residual DCE concentration (mg/L)
18

Residual DCE concentration (mg/L)

Co=1.0mg/L, 5.0 L/min
16 1.0
Co=100mg/L, 5.0 L/min
2500

)X1000
reaction
14 0.8 Co=200mg/L, 5.0 L/min
12 Co=2400mg/L, 5.0 L/min
0.6

rate constant (min-1

10

Pseudo first order

8 0.4
6 200
0.2
4
2 100 0.0
0360 0 5 10 15 20 25 30

)
Time (min)

(K
350
0

re
340

tu
1000 330 0 5 10 15 20 25 30

ra
800

pe
320

em
600
Initia 400 310 Time (min)

t
ng
l TC 200 300
A co

i
pp
ncen 0
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290

i
tratio

str
n (m

r
(a) g/L)

Ai
(b)
100 1800
Residual DCA concentration (mg/L)

Residual DCA concentration (mg/L)

90 0.5 L/min, C 0 =25mg/L 1600 0.5 L/min, C0 =700mg/L
80 1.5 L/min, C 0 =25mg/L 1.5 L/min, C0 =700mg/L
1400
70 0.5 L/min, C 0 =70mg/L 0.5 L/min, C0 =1500mg/L
1200
60 1.5 L/min, C 0 =70mg/L 0.5 L/min, C0 =1500mg/L
1000
50 0.5 L/min, C 0 =100mg/L
800
40 1.5 L/min, C 0 =100mg/L
30 600

20 400
10 200
0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
(d) Time (min)
(c) Time (min)

Fig. 3. (a) Effects of temperature and initial concentration on pseudo-first-order reaction rate constants of TCA removal; (b) removal performance of
DCE; (c–d) DCA at different initial concentrations and airflow rates by air stripping at 298 K

initial concentration of 100, 200 and 2; 400 L= min, respectively. Figs. 4(c) and 4(d) are the stripping results for model groundwater
Nearly complete DCE removal was achieved for an initial DCE samples contaminated by DCE, DCA and TCA, the only difference
concentration of 1 L= min under the same experimental conditions. being their initial concentrations. Fig. 4(c) shows that the concen-
trations of DCE, DCA and TCA decreased from 1.5, 197.0 and
DCA Air Stripping 32.0 mg=L, respectively, to below the detectable limit after 2
Fig. 3(c) and Fig. 3(d) present the stripping results for DCA at a min of air stripping. Nevertheless, as shown in Fig. 4(d), the con-
temperature of 298 K, initial concentrations of 25–1; 500 mg=L centrations of DCE, DCA and TCA decreased from 15.0, 34.0 and
and airflow rates of 0.5 and 1.5 L= min. The stripping results at 105.0 mg=L, respectively, to 0, 0.03 and 1.0 mg=L, respectively,
1.5 L= min were slightly superior to those at 0.5 L= min. For after 1 min of stripping and were all below the detectable limit after
DCA initial concentrations of 25–700 mg=L, the aqueous concen- 2 min of stripping. Vinyl chloride (VC) and monochloroethane
tration reduced to below 1 mg=L after air stripping for 10 min at an (CA), at concentrations of 0–100 mg=L, were spiked but they both
airflow rate of 1.5 L= min. A longer stripping time was required to volatilized quickly, which may be related to their lower boiling
obtain the same extent of removal at an airflow rate of 0.5 L= min. points (−13.4 and 12.3°C, respectively).
The experimental results previously described indicate that an
Combined Contaminants Stripping almost complete removal of five types of chlorinated solvents
Four groups of stripping experiments were designed to model present in groundwater can be achieved through 2 min of air strip-
groundwater samples contaminated by multiple chlorinated sol- ping at a temperature of 298 K, and airflow rates of 1.5–5.0 L= min.
vents at different concentration levels. The results are shown The stripping removal order is VC, CA, DCE, DCA and TCA,
in Fig. 4. which complies with the intervention value standards promulgated
Fig. 4(a) shows the results of air stripping for a groundwater by the Dutch Ministry of Public Housing. However, there are
sample contaminated with DCE (79.0 μg=L), DCA (85.0 μg=L) still large gaps within the target values of this standard, and further
and TCA (133; 000 μg=L). At an air flow rate of 5.0 L= min for treatment is needed.
1 min, the concentrations of DCE, DCA and TCA dropped to
0, 0 and 2; 070 μg=L, respectively, corresponding removal efficien- O3 =H2 O2 Oxidation
cies of 100, 100 and 98.4%. Likewise, for initial TCA concentra- Selecting TCE and TCA as target pollutants, ozonation experi-
tions of 159,000 and 1; 400 μg=L, after 1 min of air stripping, the ments were conducted to investigate their removal characteristics
residual concentrations were 3,270 and 7.40 μg=L, respectively. at a temperature of 298 K, pH 7.0, initial TCE and TCA concen-
When the stripping time was extended to 2 min, the concentrations trations of 10–200 mg=L, mixed O3 =O2 flow-rate of 60 L=h and
dropped to 79 and 0 μg=L, respectively, with corresponding inlet O3 concentration of 54.08 mg=L. The results are shown in
removal efficiencies up to 99.99 and 100% [Fig. 4(b)]. Figs. 5(a) and 5(b).

908 / JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / SEPTEMBER 2012

J. Environ. Eng. 2012.138:903-914.

 180000 1600
140000 90
133000 85.0 160000 159000 1400 1400
80 DCE

DCA concentration ( µg/L)

120000

TCA concentration ( mg/L)

TCA concentration ( mg/L)

70 79.0 DCA 140000 1200

Concentration ( µg/L)
100000 60 120000 1000
50 800
80000 40 100000
600
30 80000
60000 20 400
60000 200
40000 10
0 40000 7.0
0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.5 1.0 1.5 2.0
20000 Time (min) 20000 Time (min)
32.0 3270 79.0
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
(a) Time (min) (b) Time (min)
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220 120
200 197.0
180 DCE 105.0
DCA 100 DCE
TCA DCA
Concentration ( mg/L)

Concentration (mg/L)
40 80 TCA

32.0 60

20 40 34.0 1.0mg/L
0.03mg/L
20 15.0 ND
1.5 ND
0.26
0 0
0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
(c) Time (min) (d) Time (min)

Fig. 4. Effectiveness of air stripping on multiple chlorinated solvents in contaminated groundwater

Fig. 5(a) and (b) show that varying concentrations of TCE and The results shown in Fig. 5(c) and (d) indicate that addition of
TCA were removed in just a few minutes, with a faster removal rate H2 O2 enhanced removal of TCE and TCA by ozonation to some
for TCE relative to TCA. In particular, 4 and 5 min were, respec- extent. The time required to reduce the residual concentrations
tively, required to reduce residual concentrations of TCE and of TCE and TCA in solution below 1 mg=L were narrowed by ap-
TCA in solution to below 1 mg=L. The removal efficiency of TCE proximately 2 and 1 min, respectively. Better results were obtained
by ozonation was found to be higher than by oxygen flushing, with an increase in the amount of H2 O2 up to a certain critical H2 O2
although the difference in removal efficiency gradually diminished dosage level, which is consistent with results reported by Zhong
with increased initial TCE concentration. Comparable results were et al. (1998). However, further increases in H2 O2 dosage had no
obtained for TCA concerning ozonation and oxygen flushing, sug- significant effect. For TCE and TCA, the critical values of
gesting that oxygen flushing was responsible for a considerable H2 O2 were 1 and 2 ml=L, respectively. A possible reason for this
share of the removal of TCE and TCA rather than ozonation, and phenomenon was that the addition of a small quantity of H2 O2
this share increased with increasing initial concentrations of TCE could enhance the decomposition of the O3 molecule into an
and TCA. •OH radical, thus improving the removal of chlorinated solvents.
The accepted mechanisms of ozonation responsible for removal However, when the amount of H2 O2 added exceeded the critical
of organic pollutants include direct ozone molecule oxidation and dosage, the •OH radical itself could be consumed by H2 O2, thus
radical species (•OH) oxidation. These two mechanisms typically resulting in decreased removal efficiencies of the pollutants, as
differ significantly in their oxidation rates, which are related to expressed by Eqs. 1–3 (Roberto et al. 1999).
the chemical structures of oxidizable pollutants. A TCE molecule
contains one double bond that has a higher electron cloud density, 3O3 þ 2H2 O2 → 2 • OH þ 3O2 (1)
is vulnerable to molecular ozone, and can react with both ozone and
•OH with respective reaction rate constants of 17.0 and 4.0 ×
H2 O2 þ O3 → •OH þ HO2 • þO2 (2)
109 M−1 · s−1 (Hoigné et al. 1983; Buxton et al. 1988). In contrast
to TCE, the removal of TCA was primarily attributable to •OH
oxidation; therefore, its oxidation proceeded at a slower reaction
•OH þ H2 O2 → H2 O þ O2 •− (3)
rate relative to TCE. Because the ozone concentration was constant
in the tests conducted, the probability of lower concentrations of
chlorinated solvents subjected to ozone/hydroxyl radical attack
Preliminary Analysis of Ozonation Intermediates of
was much greater than that of higher concentrations of chlorinated
TCE and TCA
solvents.
To confirm the previous speculation, 1–5 ml of hydrogen Two types of intermediate TCA ozonation products were detected.
peroxide (H2 O2 ) was added into the ozonation system in an attempt The first was 1,1,1,2-tetrachloroethane (retention time 5.2 min,
to enhance the generation of •OH, thus promoting the removal of quality = 93%), and the second was 1,1-dichloro-2-propane (reten-
TCE and TCA. tion time 7.54 min, quality = 84%).

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J. Environ. Eng. 2012.138:903-914.

 1.0
Ozonation, TCA 60 mg/L 1.0 Ozonation, TCE 10 mg/L
Ozonation, TCA 150mg/L Ozonation, TCE 30 mg/L
0.8
Ozonation, TCA 200 mg/L Ozonation, TCE 157 mg/L
0.8
Air flushing, TCA 60 mg/L Air flushing, TCE 10 mg/L
0.6 Air flushing, TCA 150 mg/L Air flushing, TCE 30 mg/L
Air flushing, TCA 200 mg/L 0.6

C / C0

C / C0
Air flushing, TCE 157 mg/L
0.4
0.4

0.2 0.2

0.0 0.0
0 2 4 6 8 10 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
(a) Time / min (b) Time / min
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1.0 H2O2 0 ml/L 1.0 H2O2 0 ml/L

H2O2 1 ml/L H2O2 1 ml/L
0.8 H2O2 2 ml/L 0.8
H2O2 2 ml/L
H2O2 3 ml/L H2O2 3 ml/L
0.6 0.6

C / Co
C / Co

H2O2 5 ml/L H2O2 5 ml/L

0.4 0.4

0.2 0.2

0.0 0.0
0 2 4 6 8 10 0 5 10 15 20 25 30
(c) Time / min (d) Time / min

Fig. 5. Ozonation of (a) TCA and (b) TCE, and the O3 =H2 O2 oxidation of (c) 40 mg=L TCA and (d) 40 mg=L TCE; Experimental conditions: O3 =O2
flow rate 60 L=h, temperature 298 K and H2 O2 dose 0–5 mL=L

In addition, the concentration of chloride ion in solution increased
from the beginning of ozonation onward. It can be inferred from this
that 1,1,1,2-tetrachloroethane and 1,1-dichloro-2-propane were not
the predominant intermediates; however, identifying the exact ozo-
nation intermediates of TCE and TCA requires further investigation.
Little has been reported on the products of chlorinated solvents
by AOPs. Han et al. (2007) investigated the degradation inter-
mediates of TCE by a hybrid barrier discharge plasma process
combined with ozone decomposition catalysts. Chlorine, dichloro-
acetylchloride, trichloro-acetaldehyde and COX were detected in
the presence of oxygen whereas HCl, Cl2 , C2 H2 Cl2 , CHCl3 ,
CCl4 and C2 HCl5 were also observed. The primary by-product
was C2 HCl5 , which was generated by a chlorine radical-chain re-
action through the detachment of chlorine atom (Cl). Waldemer
et al. (2007) also found trace quantities of hexachloroethane as in-
termediates in heat-activated persulfate oxidation of TCE and PCE,
and concluded that the predominant chlorine radical species (Cl and
Cl2 •) generated by the interaction of SO•− −
4 and Cl possibly reacted
with the chlorinated ethenes or their intermediate degradation
products to produce more highly chlorinated products, as
has been reported previously for attack on chlorinated phenols
by sulfate radical (Anipsitakis et al. 2006).
From the test results described previously, we know that almost
complete oxidation of TCA and TCE can be obtained by the
O3 =H2 O2 process with the generation of trace quantities of highly
chlorinated by-products, although it cannot be precluded that some
chlorinated solvents could be removed through a stripping pathway
into effluent gas.
GAC Adsorption
Fig. 6 illustrates the adsorption breakthrough curves of gaseous
TCA by four types of GACs employing the MCRB method at
flow rates of 2.0, 3.0 and 5.0 L= min. Table 6 summarizes the
performance data for those carbons.
The results demonstrated that Shanghai coconut exhibited the
largest TCA adsorption capacity of 0.5 g=g and the other carbons,
listed as follows in decreasing order of adsorption capacity, were
Shanghai fruit >Taixi coal, 12
40 > Taixi ZJ-15, cylinder. The
explanation for this phenomenon is as follows. The pore structure
and surface chemistry of carbon particles are the most important
properties of activated carbon governing GAC’s adsorptive
capacities. Organic pollutants are most strongly adsorbed on the
internal surface areas of pores slightly larger than their effective
molecular diameter (MD), according to the microporosity effect
(Karanfil et al. 2006). Therefore, GAC’s relative capacity for
TCA adsorption was expected to be best correlated with its phenol
number, because TCA’s MD is even smaller [approximately
0.57 (Stakebake et al. 1975) versus 0.62 nm of phenol (Zhang
et al. 2007)], and both are planar and polar compounds. Indeed,
the order of GAC’s adsorption capacities for gaseous TCA (Fig. 8)
is the same as their relative phenol numbers (Table 1) of 131.0,
113.0, 76.3 and 65.1 mg=L for Shanghai coconut, Shanghai
fruit, Taixi coal (12
40) and Taixi ZJ-15 (cylinder), respectively.
Consequently, technically speaking, it is completely feasible to
employ Shanghai coconut for the fastest adsorption of exhausted
gas containing chlorinated solvents.
Coupled Process and Its Application: Case Studies
Based on the foregoing discussion, a coupled process of “air
stripping-ozonation-GAC adsorption” was proposed to provide an
alternative for contaminated subsurface, not aquifer, groundwater
remediation, because subsurface groundwater is easier to pump at
lower cost than water in an underground aquifer. The design meth-
odology of “pump-and-treat” was adopted in the coupled process.

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J. Environ. Eng. 2012.138:903-914.

 35 35
2.0 L/min 2.0 L/min
30 3.0 L/min 30 3.0 L/min
5.0 L/min 5.0 L/min

TCA vapor (mg/L)

TCA vapor (mg/L)
25 25

20 20

15 15

10 10

5 5

0 0
0 20 40 60 80 100 0 20 40 60 80
(a) Adsorption time (min) (b) Adsorption time (min)
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30 35

25 30

TCA vapor (mg/L)

TCA vapor (mg/L)

25
20
20
15
15
10
10
2.0 L/min 2.0 L/min
5 3.0 L/min 5 3.0 L/min
5.0 L/min 5.0 L/min
0 0
0 20 40 60 80 0 20 40 60
(c) Adsorption time (min) (d) Adsorption time (min)

Fig. 6. Adsorption breakthrough curves for gaseous TCA by four kinds of activated carbon: (a) Shanghai coconut; (b) Shanghai fruit; (c) Taixi coal
12
40; (d) Taixi ZJ-15 (cylinder) at a temperature of 298 K

Table 6. Summary of Breakthrough Runs for Gaseous TCA at a performed. The contaminated groundwater from the polluted sites
Temperature of 298 K of Pudong and Jiading was used in these experiments. The results
Carbon/column Flow rate Carbon TCA adsorption are illustrated in Figs. 7 and 8.
(Fig. 6) (L= min) charged (g) capacity (g=g) As Fig. 7 shows, at initial TCA concentrations of approximately
Shanghai coconut 2.0 11.80 0.50
400–1; 250 mg=L, the stripping effect at 5.0 L= min was better
3.0 11.80 0.50 than that at 1.5 L= min, with respective removal efficiencies of
5.0 11.80 0.49 95.3–99.9% and 73.3–99.3% within 30 min. Under the same
Shanghai fruit 2.0 11.80 0.19 experimental conditions, the former was higher than the latter by
3.0 11.80 0.22 0.6–22%, which was more obvious at a lower TCA concentration.
5.0 11.80 0.21 Through plotting the evolution of TCA concentration versus time
Taixi ZJ-15, cylinder 2.0 11.80 0.19 [Figs. 7(a) and 7(b)], it was found that the removal of TCA was
3.0 11.80 0.09 well-fit by a second-order exponential decay model (R2 > 0.93),
5.0 11.80 0.17
with the fitted equations shown in Table 7. Figs. 7(c) and 7(d)
Taixi coal, 12
40 2.0 11.80 0.07
3.0 11.80 0.05
illustrate the TCA concentration variations as a function of time
5.0 11.80 0.05 for an initial TCA concentration of approximately 700 mg=L in
both aqueous solution and the gas-phase as a function of time.
Similar evolution curves were observed for airflow rates of
The contaminated groundwater was first pumped into a filter, an 5.0 and 1.5 L= min. With prolonged stripping time, the aqueous
oil-water separator, to remove possible silt and oil. The pretreated TCA concentration rapidly decreased in the first 5 min, its gaseous
groundwater was then subjected to two-stage air stripping through concentration began to increase and exceeded a maximum
a rotary pump, in which volatile components present in the (65 mg=L air) at approximately 2 min, and then decreased to zero
groundwater were transferred from the water to air and collected at the end of 30 min. After subsequent O3 =H2 O2 oxidation and
in the air passage. When the concentrations of the volatile compo- adsorption by Shanghai coconut carbon, the effluent TCA concen-
nents reached stable levels, the effluent was fed to an ozonation tration was below the detection limit of GC.
reactor, in which non-volatile and semi-volatile components were The contaminated groundwater from the MW-1 well at the
effectively oxidized and eliminated. The final effluent, which had Jiading site was brown in color and had a strong pungent odor,
been treated by GACs if necessary, was recharged underground. attributable to chlorinated aromatic hydrocarbons. With the com-
After the collected gases from stripping and ozonation processes mencement of air stripping, the concentrations of chlorinated sol-
were dehumidified and adsorbed, the off-gas was evacuated vents, i.e., cis-DCE, TCE and PCE, decreased from 9,270, 3,530
directly into the atmosphere. and 178,000 μg=L, respectively, to 10, 180 and 300,300 μg=L,
To verify the feasibility and effectiveness of the proposed respectively, after a stripping time of 10 min at an airflow rate of
coupled process, small-scale laboratory experiments were 5.0 L= min and a temperature of 298 K [see Fig. 8(a)].

JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / SEPTEMBER 2012 / 911

J. Environ. Eng. 2012.138:903-914.

 450 1400
1.5 L/min 1251.12 1.5 L/min
400 401.62 1200 1184.97
5.0 L/min 5.0 L/min

TCA concentration (mg/L)

TCA concentration (mg/L)
1000
350
317.88 800 28.35
300 85.16
140 137.88 4.29 600 3.8
120 3.87
100 433.03 3.31
1.58 400 0.97
80 70.59 1.0
60 195.1
40 48.5 200 104.4
7.56 1.16 1.09 22.30 10.90 7.94
20 21.33 11.4 10.3 0.99 7.91 69.88 0.97 0.94 0.85
0 0
0 4 8 12 16 20 24 28 32 0 5 10 15 20 25 30
(a) Time (min) (b) Time (min)
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Gaseous TCA concentration (mg/L air)

80
700 100
Aqueous TCA concentration (mg/L)

70 1.5 L/min
600 1.5 L/min

TCA removal efficiency (%)

80 3.0 L/min
5.0 L/min 60
500 TCA removal efficiency at 1.5 L/min
50
TCA removal efficiency at 5.0 L/min 60
400
40
300 40 30
200 20
20
100 10
0 0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
(c) Time (min) (d) Time (min)

Fig. 7. Evolution of TCA concentration versus time in aqueous solution at initial concentrations of approximately (a) 400; (b) 1,250; (c) 700 mg=L, in
addition to (d) off gas, for the contaminated groundwater from Pudong, Shanghai; experimental conditions: airflow rate 1.5 and 5.0 L= min, tem-
perature 298 K

3.0 0 min
Contaminant concentration ( µg/L)

1 min
178000 2.5 2 min
4 min
Absorbance

Air stripping Ozonation 2.0 6 min

cis-DCE 9 min
35000 1.5
TCE 12 min
30000 PCE
25000 1.0 15 min
20000 2-CP
15000 20 min
10000 0.5
5000
0
-5000 0.0
0 5 10 15 20 25 30 200 300 400 500 600
(a) Time (min) (b) λ (nm)

(c)

Fig. 8. (a) Variations of contaminants; (b) UV-visible spectra; (c) color as a function of time for the contaminated groundwater from Jiading,
Shanghai; experimental conditions: airflow rate 5.0 L= min, temperature 298 K, ozone concentration 54.08 mg=L, and O3 =O2 flow rate 60 L=h

912 / JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / SEPTEMBER 2012

J. Environ. Eng. 2012.138:903-914.

 Table 7. Fitted Equations for TCA Removal by Air Stripping from the Pudong Site
Flow rate L= min and initial
TCA concentration (mg=L) The fitted equations by second-order exponential decay model R2
1.5, 401.6 Y ¼ 156.67414 Expð−X=0.31249Þ þ 235.77716 Expð−X=1.52113Þ þ 9.17144 0.999
5.0, 317.9 Y ¼ 157.91953 Expð−X=0.24796Þ þ 157.91953 Expð−X=0.24796Þ þ 2.04025 0.999
1.5, 1,251 Y ¼ 154.4675 Expð−X=4.88089Þ þ 1; 089.58925 Expð−X=0.77538Þ þ 7.1266 0.999
5.0, 1,184 Y ¼ 436.78932 Expð−X=0.00653Þ þ 436.78932 Expð−X=0.00653Þ þ 28.87052 0.931

However, the concentration of 2-CP remained unchanged, leaving
the groundwater darkly colored [see sample 2-0 in Fig. 8(c)]. Dur-
ing the air stripping step, large quantities of foam were generated
and resulted in a sharp rise of the liquid level of the stripping
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ozonation as the oxidative process for the removal of TCE and
PCE. Reloading and regeneration of saturated GAC is also a
challenge. In future research, a series of pilot-scale tests on-site
will be conducted to verify the effectiveness of the coupled process,

instrument, thus significantly reducing the stripping efficiencies
of chlorinated solvents. In the subsequent ozonation step, an in-
crease in ozonation time led to a decrease in 2-CP concentration
with a first-order kinetic rate constant of 0.7893 min−1
(R2 > 0.99), and complete disappearance of 2-CP at 22 min. The
UV-visible spectra of the ozone-treated groundwater are shown in
Fig. 8(b). The primary peak was at 233 nm and the intensity of the
peak decreased as the ozonation time was increased. After 9 min
of treatment, the peak decreased by 85.7% (the initial absorbance
value of 2.868 decreased to 0.41), which is attributable to frag-
mentation of 2-CP into smaller-molecular-weight organic inter-
mediates that absorb less UV-V is light. The color of the
solution also underwent a distinct change with reaction time, as
seen in Fig. 8(c). However, the oxidation rates of TCE and
PCE in μg levels were so low that there was still residual TCE and
PCE in the solution, at concentrations of 0.6 and 5.0 μg=L,
respectively, even after 30 min of ozonation. These results indicate
that ozone-treated effluent needs to be treated by AC adsorption
before it is discharged underground.
Pump-and-treat (P&T) remediation of groundwater contamina-
tion is one of the most commonly used and mature groundwater
remediation technologies, conducted or planned at many sites
around the world. According to the Superfund Remedy Report
of 2010 issued by the U.S. EPA (2010), in the four fiscal years
2005–2008, P&T was identified as a remedy component in 22,
20, 23 and 18 groundwater decision documents, respectively, or
28, 21, 24 and 28% of 79, 97, 95 and 65 groundwater decision
documents, respectively. These numbers indicate that the selection
of P&T by Superfund projects has leveled off. Since the beginning
of the 1980s, some Western countries, such as the United States,
have initiated groundwater remediation. For example, the US
federal government spent US$3–8 billion annually on the
treatment and remediation of hazardous abandoned sites under
Superfund. By 2004, this program had funded treatment of 864
contaminated sites, and over 1.4 billion cubic meters of hazardous
liquids, groundwater and surface water had been remediated
(Zhang et al. 2006). In China, however, remediation of contami-
nated groundwater is a new research field that is still in its infancy.
Therefore, remediation technologies and equipment with indepen-
dent intellectual property urgently needs to be researched and
developed.
The coupled process proposed in this paper is intended for use in
quick removal of volatile and non-volatile toxic contaminants
present in groundwater. There are still opportunities to further op-
timize the experimental conditions and processes of the coupled
process. For example, the tendency of chloroethenes to undergo
reductive dechlorination decreases with a decreasing number of
chlorine substituents, whereas with fewer chlorine substituents,
chloroethenes more easily undergo oxidative degradation (Tiehm
et al. 2011). In this respect, it is not the best option to choose
improve the process as needed, and lay a solid foundation for
the construction of mobile installations for use in the field.
Conclusions
The results of this study demonstrate the feasibility and effective-
ness of the coupled process described in this paper, which includes
air stripping, advanced oxidation, and GAC adsorption for treat-
ment of groundwater polluted by volatile chlorinated hydrocarbons
alone or in combination with other non-volatile aromatic hydrocar-
bons. The following conclusions were drawn:
1. At a higher airflow rate (i.e., 5.0 L= min), air stripping was a
more effective means of treating contaminated groundwater
containing volatile chlorinated solvents. Nearly complete
removal of isolated TCE, TCA, DCE and DCA was observed
for initial concentrations of several tens to thousands of mg=L
within several minutes at room temperature. In air stripping of
combined contaminants, the stripping order was VC, CA,
DCE, DCA and TCA, which may be related to their vapor
pressures and Henry’s constants. When the concentrations
of TCE, TCA, DCE and DCA in aqueous solution were lower
than 1 mg=L, further extending the stripping time had little
effect on removal efficiency.
2. The results of 10–200 mg=L of TCE and TCA ozonation in-
dicated that the removal effect of chlorinated solvents included
ozone oxidation and oxygen flushing, and the latter contribu-
tion decreased with decreasing concentrations of TCE and
TCA. The addition of H2 O2 enhanced, to some extent, the
removal of TCE and TCA by ozonation; optimal dosages
were 1 and 2 mL, respectively.
3. For all four types of GAC studied, their gaseous TCA adsorp-
tion capacities were correlated with their phenol number in
the following order: Shanghai coconut, Shanghai fruit, Taixi
coal (12
40) and Taixi ZJ-15 (cylinder), with the largest
TCA adsorption capacity being 0.5 g=g.
4. For TCA-contaminated groundwater at the Pudong site,
when the initial concentrations of TCA varied between
400–1200 mg=L, 95.3–99.9% of TCA was removed from
the groundwater by air stripping and thereafter was adsorbed
by Shanghai coconut carbon. The rest was partly oxidized by
the O3 =H2 O2 process. For groundwater contaminated by cis-
DCE (9270 μg=L), TCE (3530 μg=L), PCE (178000 μg=L)
and 2-CP (21600 μg=L) at the Jiading site, a stripping time
of 10 min with an airflow rate of 5.0 L= min and a temperature
of 298 K removed 99.9, 99.5 and 99.8%, respectively, of these
contaminants. Complete elimination of 2-CP was observed
in the ozonation process. Employing the proposed coupled
process, the contaminated groundwater samples from the
Pudong and Jiading sites were successfully treated, and the
effluent complied with the target values that are standard

JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / SEPTEMBER 2012 / 913

J. Environ. Eng. 2012.138:903-914.

 for groundwater set forth by the Dutch Ministry of Public
Housing, indicating that the coupled process is a viable meth-
od for remediating contaminated groundwater containing
chlorinated solvents efficiently and effectively.
Acknowledgments
Funding for this work was provided by the National Natural
Science Foundation of China (Grant No. 40901148, 20807028);
the National Environmental Protection Public Welfare Science
and Technology Research Program of China (Grant No.
201109013); the Shanghai Postdoctoral Sustentation Fund, China
(Grant No. 11R21412500); and the National Science Foundation
Downloaded from ascelibrary.org by New York University on 05/16/15. Copyright ASCE. For personal use only; all rights reserved.
for Postdoctoral Scientists of China (Grant No. 20110490683).
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