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Article
Light-Source-Dependent Effects of Main Water Constituents on
Photodegradation of Phenicol Antibiotics: Mechanism and Kinetics
Linke Ge, Jingwen Chen, Xianliang Qiao, Jing Lin, and Xiyun Cai
Environ. Sci. Technol., 2009, 43 (9), 3101-3107• DOI: 10.1021/es8031727 • Publication Date (Web): 30 March 2009
Downloaded from http://pubs.acs.org on May 14, 2009

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 Environ. Sci. Technol. 2009, 43, 3101–3107

been reported for Danish fish farms and adjacent water bodies
Light-Source-Dependent Effects of (5). Investigating the environmental transformation of these
Main Water Constituents on pollutants is necessary to enable accurate ecological risk
assessments of phenicols.
Photodegradation of Phenicol Solar photodegradation is a major transformation pathway
for organic pollutants in the environment (6, 7). Several
Antibiotics: Mechanism and Kinetics pharmaceuticals, including tetracycline (8), oxytetracycline
(9), citalopram (10), mefenamic acid (11), nitrofuran anti-
LINKE GE, JINGWEN CHEN,* biotics (12), and -blockers (13) were found to undergo
XIANLIANG QIAO, JING LIN, AND photodegradation. However, studies on environmental trans-
XIYUN CAI formations of phenicols are sparse. We performed a literature
Key Laboratory of Industrial Ecology and Environmental
survey and found only two relevant studies. Pouliquen et al.
Engineering (MOE), Department of Environmental Science (9) investigated hydrolysis and photolysis of four antibacterial
and Technology, Dalian University of Technology, agents (including florfenicol) in deionized water, freshwater
Linggong Road 2, Dalian 116024, P. R. China and seawater, and found florfenicol was resistant to photolysis
under irradiation at λ ) 300-800 nm. Hayes et al. (14) assessed
the stability of florfenicol in drinking water and found that
Received November 10, 2008. Revised manuscript received
aqueous solutions were stable when shielded from light.
February 27, 2009. Accepted March 6, 2009.
Organic pollutants can undergo direct photodegradation
resulting from the direct absorbance of photons, as well as
indirect photodegradation initiated by light absorption by
Thiamphenicol and florfenicol are two phenicol antibiotics other chemicals in the system (15, 16). Many aquatic
constituents, such as humic acids (HA), Cl-, Br-, I-, Fe(III),
commonly used in aquaculture. Photodegradation experiments
NO3-, and CO32- etc., can act as sensitizers to promote the
on these phenicols were performed in aqueous solutions indirect photodegradation (17-19). Self-sensitized photo-
under irradiation of different light sources. We found under oxidation of pharmaceuticals, e.g., tetracycline (8, 21),
UV-vis irradiation (λ > 200 nm) they photodegraded the fastest indocyanine green (21), and 1-benzyl-3,4-dihydroisoquino-
in seawater, followed by pure water and freshwater, whereas lines (22) has also been reported. In self-sensitized photo-
under solar or simulated sunlight (λ > 290 nm), they oxidation, chemicals are oxidized by singlet oxygen (1O2)
photodegraded in freshwater only. The effects of Cl- (the produced via the energy transfer from the light-excited triplet
dominant seawater constituent), humic acids (HA, main state of the compounds to ground state 3O2 (20, 23).
constituents in freshwater) and other water constituents on In previous studies, HA were observed to either accelerate
the photodegradation of the antibiotics as a function of different or inhibit the photodegradation of organic chemicals (24-27).
In some cases, the direction of the HA effect is dependent
light sources were studied so as to interpret the light-source-
on the irradiation characteristics. For example, photolysis of
dependent effects of different waters. Under UV-vis atrazine was enhanced by HA when irradiated with λ )
irradiation, Cl- was found to promote singlet oxygen (1O2) 280-480 nm light, but was inhibited upon irradiation with
formation and accelerated the photodegradation of phenicols, a mercury-lamp having a prominent emission band around
whereas the phenicols did not photolyze under simulated 254 nm (28, 29). Likewise, Cl-, as a dominant constituent of
solar irradiation, irrespective of Cl-. In contrast, the presence seawater, sometimes accelerated and at other times inhibited
of HA inhibited phenicol photolysis under UV-vis irradiation photodegradation of organic pollutants (26, 27, 30-32).
through competitive photoabsorption, but HA photosensitized In this study, we also observed that the effects of
degradation under simulated solar irradiation. Under UV-vis prominent water constituents (i.e., HA and Cl-) on the
irradiation, the wavelength-averaged (200-290 nm) quantum photodegradation of florfenicol and thiamphenicol were
dependent on the light sources used. Thus, the focus of the
yields for thiamphenicol and florfenicol in pure water were 0.022
study was to elucidate the light-source-dependent effects.
( 0.001 and 0.029 ( 0.001, respectively. Their solar photolytic Intermediates and degradation products were identified and
half-lives in freshwater were 186 ( 17 h and 99 ( 16 h, employed to explain the degradation pathways. To the best
respectively. UV-vis photodegradation intermediates were of our knowledge, this is the first comprehensive report on
identified by HPLC-MS/MS, and degradation pathways were the photochemical behavior of these two representative
proposed. These involve photoinduced hydrolysis, dechlorination, phenicol antibiotics and on the interpretation of the dual
self-sensitized photo-oxidation process via 1O2, and chlorination. effects of water constituents on the phenicol photodegra-
These results are of importance toward the goal of assessing dation kinetics. Here dual effects refer to that one water
the persistence of phenicols in wastewater treatment and the constituent like HA or Cl-, behaves two different effects on
environment. the photodegradation.

Experimental Section
Introduction Chemicals. Thiamphenicol and florfenicol were provided
Phenicol antibiotics (e.g., florfenicol and thiamphenicol) are by Zhejiang Hisoar Pharmaceutical Co., Ltd. with 99.28 and
widely approved for aquacultural use in China, Canada, 99.26% purity, respectively. Humic acid (HA, Fluka no. 53680)
Japan, Korea, and Europe (1, 2) and have been detected in was purchased from Sigma Aldrich, Inc. (Milwaukee, WI),
numerous biological samples (3, 4), especially in aquatic for which the characteristic parameters were reported
products. Florfenicol concentrations of 0.002-1 µg/L have previously (33, 34). All organic solvents were purchased from
Tedia Company, Inc. (HPLC grade). Other chemical reagents
* Corresponding author phone/fax+86-411-84706269; e-mail: were of analytical grade and used as received. Ultra pure
jwchen@dlut.edu.cn. water was obtained with a Millipore-Milli Q system. Fresh-
10.1021/es8031727 CCC: $40.75  2009 American Chemical Society VOL. 43, NO. 9, 2009 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 3101
Published on Web 03/30/2009
 description of the EPR determination, refer to the Supporting
Information. NaN3 and isopropanol were also added to the
photoreaction solutions to assess the presence of 1O2 and
•OH. NaN3 and isopropanol are quenchers for 1O2 and •OH,
respectively, and have been used frequently in photochemical
studies to investigate reaction mechanisms (18, 36, 37). The
effects of pH and ionic strength on the photoreaction kinetics
were examined using phosphate buffers and Na2SO4 to adjust
pH and ionic strength, respectively.
Dark controls shielded from light were performed sim-
ultaneously under the same conditions. In addition, the
phenicol solutions were preserved in the dark for up to 50
days at room temperature to examine their aqueous stability.
Photodegradation experiments and the dark controls were
carried out in triplicate.
Analytical Determinations and Product Identification.
Initial and residual concentrations of the phenicols were
analyzed by an Agilent 1100 HPLC with a DAD. Degradation
intermediates and products were analyzed by an Agilent 1100
Series LC/MSD trap system using a triple quadrupole mass
analyzer and working in positive and negative mode. Total
organic carbon (TOC) was measured with a Shimadzu TOC-
VCPH analyzer. Anions were analyzed with a Shimadzu Class-
VP ion chromatography. Cations were monitored by induc-
FIGURE 1. Ultraviolet absorption spectra of the two model
tively coupled plasma-atomic emission spectrometry (Optima
compounds and irradiance spectra of the light sources. Thia-
2000 DV). Detailed descriptions on sample pretreatment and
mphenicol and florfenicol were dissolved in water.
instrumental analysis are presented in the Supporting
water and seawater were collected from a local reservoir and Information.
the Yellow Sea, respectively, filtered by 0.22 µm filters, and
stored at -20 °C until use. They were used within 30 days, Results and Discussion
and measured constituents listed in Table S1 in the Sup- Photolytic Kinetics and Quantum Yields in Pure Water. No
porting Information did not changed significantly during obvious loss of the two phenicols was observed in the dark
storage. Local humic acids (L-HA) were extracted from the controls, thus the decay from other processes was negligible.
freshwater of the local reservoir following the method Upon preserving the dark control solutions for up to 50 days
recommended by the International Humic Substances at room temperature, the thiamphenicol concentrations
Society (http://www.ihss.gatech.edu/). decreased by 5.9, 1.9, and 5.4%, in pure water, freshwater,
Photodegradation Experiments. Three kinds of light and seawater, respectively; and 2.1, 5.3, and 6.2%, respectively
sources were employed to perform the photolysis experi- for florfenicol. Thus, the two phenicol antibiotics are hy-
ments, (a) UV-vis irradiation (λ > 200 nm) simulated by a drolytically stable and possess a hydrolysis half-life greater
300 W high-pressure mercury lamp immersed inside a water- than one year at 25 °C in natural waters, which is consistent
cooled quartz well, (b) sunlight (λ > 290 nm), and (c) simulated with previous studies (9, 14, 38).
sunlight (λ > 290 nm) by a pyrex-well cooled and filtered The two compounds dissolved in pure water did not
xenon lamp (1000 W). The light source irradiance spectra photolyze under irradiation of sunlight or simulated sunlight
(Figure 1) were measured with a monochromator (Acton, (λ > 290 nm) (Figure 2), which was expected since they do
SP-300), and the absorption spectra (Figure 1) of the two not absorbe ligh at λ > 290 nm and thus cannot undergo
antibiotics were measured by a Hitachi U-2800 spectropho- direct photolysis (Figure 1). These results are consistent with
tometer. The light intensities (200-420 nm) in the center of the observations of Pouliquen et al. (9).
the reactive solutions were 4.10 mW/cm2, 7.37 mW/cm2 and In contrast, the phenicols photolyzed quickly when
0.83 mW/cm2, for the mercury lamp, sunlight, and xenon dissolved in pure water and exposed to UV-vis irradiation
lamp, respectively. (λ > 200 nm), which includes the 200-290 nm wavelengths
An XPA-1 merry-go-round photochemical reactor in addition to what is observed to natural sunlight (Figure
(Xujiang Electromechanical Plant, Nanjing, China) with 2). Linear relationships between ln(C/C0) and time (t) showed
quartz tubes containing the reaction solutions was used that photodegradation reactions followed the pseudofirst-
for the photodegradation experiment under UV-vis and order kinetics (r2 > 0.95). The photodegradation rate constants
simulated sunlight irradiation. Samples were exposed to (k), half-lives (t1/2) and r2 are listed in Supporting Information
solar irradiation on a building’s terrace in Dalian (38°53′ Table S2. In pure water and under irradiation of UV-vis, the
N, 121°31′ E) from July to August of 2007. Quartz tubes t1/2 for thiamphenicol and florfenicol were 17 ( 0.8 min
containing the solutions were held approximately 45° from and 14 ( 0.6 min, respectively. Their wavelength-averaged
the horizon, and exposed to clear sunshine from 9:00 to (200-290 nm) quantum yields were determined to be 0.022
16:00. The total sunlight exposure time was 84 h. Quantum ( 0.001 and 0.029 ( 0.001, respectively.
yields in pure water were measured with UV-vis irradiation Photodegradation Mechanisms and Pathways. The EPR
and by potassium ferrioxalate actinometry (35). measurements for the phenicols in pure water under UV-vis
To elucidate the effects of the main seawater and irradiation indicated that photosensitized generation of 1O2
freshwater constituents (Cl-, HA, L-HA) on the photodeg- occurred, rather than •OH or O2•- (Supporting Information
radation kinetics as a function of different light sources, the Figure S3). Furthermore, the addition of NaN3 in pure water
reagents were added to the reaction solutions within their induced a pronounced retardation of their photodecompo-
normal levels in the field. Electron paramagnetic resonance sition rate under UV-vis (λ > 200 nm) irradiation, whereas
(EPR) spectroscopy was employed to determine photosen- isopropanol had little effect on the photolysis rate (Figure 3).
sitized reactive oxygen species (ROS), such as 1O2, superoxide Thus, it can be inferred that the photoreactions of the two
anion (O2•-), and hydroxyl radical (•OH). For detailed phenicols involved the self-sensitized photo-oxidation pro-

3102 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 43, NO. 9, 2009

FIGURE 2. Degradation kinetics of thiamphenicol (a) and florfenicol (b) in waters under solar (λ > 290 nm), simulated solar (λ > 290
nm), and UV-vis (λ > 200 nm) irradiation.

FIGURE 3. Effects of NaN3 (5 mM) and isopropanol (100 mM) on UV-vis (λ > 200 nm) photodegradation kinetics of thiamphenicol and
florfenicol in pure water.

cess via 1O2, and the UV-vis photodegradation in pure water (λ > 200 nm) degradation of the phenicols dissolved in pure
did not involve •OH. water, we also identified Cl- and small molecule acids (e.g.,
Addition of NaN3 and isopropanol might have an impact formic acid). F- was detected for florfenicol. From the
on pH and ionic strength of the reaction solutions. Therefore, photoproducts, their photolysis pathways are proposed
the effects of matrix pH and ionic strength on the photo- (Figure 4). The isomerides in Figure 4 could be formed due
reactions were further investigated. It was observed that t1/2 to the different substituent position of sCdO and sOH group
of thiamphenicol and florfenicol was not affected by the and their most possible structures are shown.
solution pH (p > 0.05) (Supporting Information Table S2), It is apparent that the photolysis pathways for the two
which is reasonable since the functional groups of the two phenicols are similar. According to the product identification,
phenicols were not ionized in the pH range 5-11 (39). In they could undergo four reactions: photoinduced hydrolysis,
addition, we found that addition of Na2SO4 did not affect the photo-oxidation, dechlorination, and photoinduced chlo-
t1/2 of thiamphenicol and florfenicol (Supporting Information rination. These reaction types were also reported in the
Table S2), thus the photolysis kinetics were independent of literature for the photodegradation of other compounds
Na+, SO42-, and ionic strength. (40-43). The photoinduced hydrolysis reaction led to product
In total we identified eight byproducts for thiamphenicol I for thiamphenicol, and product I’ and IV’ for florfenicol,
and six for florfenicol (Supporting Information Table S4). which were combined with the dechlorination reactions
Their total ion chromatograms and mass spectra are provided leading to VII and V’. Product VI came from reductive
in Supporting Information Figures S5 and S6. For 6 h UV-vis dechlorination of thiamphenicol. However, the correspond-

VOL. 43, NO. 9, 2009 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 3103

FIGURE 4. Proposed transformation pathways for UV-vis (λ > 200 nm) photodegradation of thiamphenicol and florfenicol in pure
water.

ing product for florfenicol was not detected. The photo- kinetics with respect to the different light sources. As shown
oxidation was mediated by 1O2, and happened at the different in Figure 5, addition of Cl- to pure water increased the
carbon atoms in the molecules of the parent compounds photolytic rate of the two compounds under UV-vis ir-
and resulted in the formation of the isomers. The photo- radiation (λ > 200 nm), whereas simulated solar irradiation
induced chlorination reaction, replacing the methylsulfonyl (λ > 290 nm) was incapable of photolyzing the antibiotics
group by sCl, led to product VIII and VI′. irrespective of Cl-. Thus, the effects of Cl- on the photo-
Dual Effects of Water Constituents with Different Light degradation were dependent on the light sources used.
Sources. When irradiated by UV-vis (λ > 200 nm), the two As shown in Supporting Information Table S3, under
phenicols underwent photodegradation in the three waters, UV-vis irradiation (λ > 200 nm),
with rates in seawater being the fastest, followed by pure
water and freshwater (Figure 2). However, under sunlight or kPW + Cl- > kPW (1)
simulated sunlight (λ > 290 nm) irradiation, photolysis
occurred in freshwater only (Figure 2). The solar photolytic kPW + Cl- + NaN3 ) kPW + NaN3 (2)
t1/2 of thiamphenicol and florfenicol in freshwater were 186
( 17 h and 99 ( 16 h, respectively (Supporting Information where kPW and kPW + Cl- are rate constants (k) for phenicol
Table S2). From these observations, it can be concluded that photolysis in pure water and in Cl- containing aqueous
the photodegradation kinetics of the phenicols are dependent solutions, respectively; kPW + NaN3 and kPW + Cl- + NaN3 correspond
on the light-source characteristics, as well as the different to the rate constants for sole addition of NaN3 in pure water
water constituents in seawater and freshwater. and joint addition of Cl- + NaN3, respectively. As NaN3 is a
As Cl- is the most abundant ion in seawater, we quencher for 1O2, eq 2 indicates that Cl- does not enhance
investigated the effects of Cl- on the photodegradation phenicol photolysis if the reaction does not involve 1O2. With

3104 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 43, NO. 9, 2009

FIGURE 5. Effects of Cl-, Sigma-Aldrich humic acid (HA) and local humic acid (L-HA) on photodegradation rate constants (k) of
thiamphenicol and florfenicol under UV-vis (λ > 200 nm) and simulated sunlight (λ > 290 nm) irradiation.

the addition NaN3, the rate constants of 1O2-induced than visible light (Supporting Information Figure S2). Al-
photolysis without and with Cl- addition, k1O2(PW) and though HA could also sensitize photodegradation, the
k1O2(PW + Cl-), respectively, can be calculated by eqs 3 and 4, experimental results indicated that photosensitization played
respectively. a secondary role. Light attenuation by HA has also been
reported in previous studies (48-51). This study shows that
k1O2(PW) ) kPW - kPW + NaN3(without Cl-) (3) HA can have a dual effect, which is dependent on the light
sources used.
k1O2(PW+Cl-) ) kPW + Cl- - kPW + Cl- + NaN3(with Cl-) Besides Cl- and HA, we also investigated the roles of other
(4) environmentally relevant aqueous constituents under ir-
radiation of simulated sunlight (λ > 290 nm) and UV-vis
Deducting eq 2 from eq 1, we obtain (λ > 200 nm). Fe(III), NO3-, HCO3-, I-, and Br- did not induce
kPW - - kPW - > kPW - kPW (5) the photodegradation of the two phenicols under simulated
+ Cl + Cl + NaN3 + NaN3
solar irradiation (λ > 290 nm). However, these constituents
impacted photodegradation under UV-vis irradiation
Thus, from eqs 3-5 it can be deduced that
(λ > 200 nm). Supporting Information Table S2 shows that
k1O2(PW+Cl-) > k1O2(PW) (6) Fe(III), NO3-, HCO3- and I- inhibited photodegradation rates
to some extent, while Br- evidently accelerated the photolytic
reactions. The inhibitive effects of Fe(III), NO3- and HCO3-
Equation 6 indicates that under UV-vis irradiation (λ > 200
nm), Cl- increased the rate of 1O2-induced indirect photolysis. could be mainly due to their photoshielding effects. Under
Thus, Cl- promoted the formation of 1O2, and the promotion UV-vis irradiation (λ > 200 nm), Br- and I- might have a
effect was also supported by the EPR measurements (Sup- similar reaction mechanism as Cl-. However, we observed
porting Information Figure S3). However, when irradiated that I- could be easily photooxidated to I2, which colored the
by simulated sunlight, the process of 1O2 generation was not reactive solutions and thus exhibited the light-filtering effect.
involved due to the lack of absorption at λ > 290 nm. Although other water constituents may also affect the
Therefore, solar photolysis did not occur even with the photodegradation kinetics of the phenicols, this study showed
addition of Cl-. that Cl- and HA, the most abundant dissolved species in
We observed different effects of HA: inhibition of the seawater and freshwater, respectively, explained most of the
phenicol photodegradation under UV-vis irradiation light-source-dependent effects of the different waters.
(λ > 200 nm) and acceleration under simulated sunlight Environmental Significance. Since the representative
(λ > 290 nm) (Figure 5). The local humic acids (L-HA) also phenicols in this study are primarily employed in aquaculture,
displayed the similar dual effects with respect to different fresh and marine waters are an important first point of entry
light sources (Figure 5). into the environment. It was found that the phenicols in
As shown in Supporting Information Figure S2, HA and freshwater underwent HA-sensitized photoreactions under
L-HA absorb UV-vis from 200 to 700 nm. Under simulated the solar irradiation, which is of importance to the fate
solar irradiation (λ > 290 nm), although the two phenicols assessment of these antibiotics. Furthermore, solar degrada-
did not undergo direct photolysis due to the lack of absorption
tion rates were faster in freshwater than in seawater, sug-
at λ > 290 nm, we observed by EPR that HA photosensitized
gesting that their movement from freshwater to estuaries,
generation of 1O2 (Supporting Information Figure S3), and
which generally have lower HA levels, may result in decreased
thus, HA initiated the photosensitization degradation. The
HA photosensitized degradation products (λ > 290 nm) are degradation rates and enhance accumulation, which may
shown in the dashed boxes of Figure 4. Photosensitized pose risks to aquatic ecological systems. The phenicols were
production of 1O2 by HA has also been observed in many also found to photodegrade quickly under UV-vis irradiation
previous studies (44-47). These observations explained the (λ > 200 nm), which suggests that UV-vis irradiation could
acceleration effects of HA on the photodegradation of the be used to remediate phenicol pollution in aquaculture
phenicols under simulated sunlight (λ > 290 nm). wastewater, given that UV-vis irradiation is widely used for
Under UV-vis irradiation (λ > 200 nm), the retarding disinfection of aquaculture systems. The remediation method
effects of HA are likely due to competitive absorption of short- is specially suitable to saltwater as Cl- was proved to catalyze
wavelength photons (λ < 290 nm) since HA absorb more UV the reaction.

VOL. 43, NO. 9, 2009 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 3105

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