Environ Sci Pollut Res (2011) 18:12431252 DOI 10.

1007/s11356-011-0457-9

RESEARCH ARTICLE

Factors that have an effect on degradation of diclofenac in aqueous solution by gamma ray irradiation
Qun Liu & Xingzhang Luo & Zheng Zheng & Binguo Zheng & Jibiao Zhang & Yongjun Zhao & Xiaoying Yang & Jiaqi Wang & Lianhong Wang

Received: 24 August 2010 / Accepted: 24 January 2011 / Published online: 5 March 2011 # Springer-Verlag 2011

Abstract Purpose Gamma ray irradiation is considered as an effective way to degrade diclofenac. However, due to the extensive coexisting substances in natural waters, the use of gamma ray irradiation for degradation is often influenced by multiple factors. The various factors that affect degradation efficiency, such as initial diclofenac concentration, initial pH, and the concentration of the additives including H2O2 (OH radical promoter), CH3OH (OH radical scavenger), thiourea (OH, H, and eaq scavenger), humic acid, and NO3 (coexisting substances in natural waters), are investigated. Furthermore, possible intermediate products are identified and corresponding transformation pathways are proposed. Methods Degradation experiments were performed in a 50-mL airtight Pyrex bottle loaded with 25 mL of diclofenac solutions at various initial concentrations of 20.5, 30.4, and 50.1 mg L1. The radiation doses were controlled at 0, 0.3, 0.5, 0.7, and 1.0 kGy. Results Study results indicate that: (1) The degradation efficiency of diclofenac decreases with the increase of its

initial concentration. (2) The degradation efficiency is higher under acidic conditions than in neutral and alkaline media. (3) The results obtained when H2O2, CH3OH, and thiourea were added show that the degradation of diclofenac takes place via two pathways: oxidation by OH radicals and reduction by eaq and H. (4) The extensive coexisting substances in natural waters, such as humic acid and NO3, do not affect the degradation efficiency. Based on the identified intermediates, it is proposed that transformation pathways are initiated mainly by H, eaq, and OH. Conclusion Gamma ray irradiation effectively degrades diclofenac. Keyword Diclofenac . Gamma ray irradiation . Degradation . Factors . Transformation pathways

1 Introduction Pharmaceuticals and personal care products (PPCPs), which have long been used globally, are of great concern for their potential ecological and environmental impacts (Buser et al. 1999; Weigel et al. 2004; Loraine and Pettigrove 2006; Kim et al. 2007; Kosjek et al. 2008; Benotti et al. 2009; Mcclellan and Halden 2010). PPCPs are widely used and discharged in large quantities. Although PPCPs are in extremely low concentrations in aquatic environments, most of them are biologically active, and they can affect aquatic organisms and sometimes have unpredictable biochemical interactions when they mix with each other. Furthermore, they could accumulate along the food chain. Diclofenac is a typical PPCP commonly used as an analgesic, antiphlogistic, and antirheumatic in the treatment of inflammatory and painful diseases of rheumatic or non-rheumatic origin. In general, 15% of diclofenac is unconsumed and released from human bodies, and it ultimately enters the wastewater treatment

Responsible editor: Philippe Garrigues Q. Liu : B. Zheng : J. Zhang : J. Wang : L. Wang State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210093, Peoples Republic of China Q. Liu e-mail: ldqun@yahoo.com.cn X. Luo : Z. Zheng (*) : Y. Zhao : X. Yang Department of Environmental Science and Engineering, Fudan University, 220 Handan Road, Shanghai 200433, Peoples Republic of China e-mail: zzhenghj@fudan.edu.cn X. Luo e-mail: xzluo@nju.edu.cn

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systems. Although diclofenac is relatively low in ecotoxicity, its toxic effects have been demonstrated to increase considerably in combination with other pharmaceuticals in water, even at minute concentrations (Cleuvers 2004). In addition, conventional technologies employed in communal sewage treatment plants are inefficient in removing diclofenac for their lipophilic and biologically persistent action (Joss et al. 2006; Lishman et al. 2006; Zhang et al. 2008a; Stlten et al. 2008; Radjenovi et al. 2009; Monteiro and Boxall 2010; Rosal et al. 2010). Therefore, as effective technologies, advanced oxidation processes (AOPs) represent a good method for wastewater treatment. Different chemical oxidation methods for degrading diclofenac have recently been described, such as Fenton reactions, sonolysis in the presence of catalysts, ultrasound in the presence of photocatalysts, and UV-light irradiation in the presence of H2O2 or ozone (Ravina et al. 2002; Huber et al. 2003; Vogna et al. 2004; Lenidas et al. 2005; Prez-Estrada et al. 2005; Hartmann et al. 2008; Vincenzo et al. 2009; Madhavan et al. 2010; Gyer and Ince 2011). As an AOP, gamma ray irradiation is an effective way for degrading organic compounds due to its high penetrating power and the isothermal character (Yamazaki et al. 1983; Kimura et al. 2006; Zhang et al. 2008b; Ito et al. 2009; Choi et al. 2010). By exposure to gamma rays, radiolysis initially occurs to produce some reactive primary species such as hydroxyl radicals, hydrogen atoms, hydrated electrons, and hydrogen ions, which are responsible for the degradation of the pollutants. However, due to operating parameters and the extensive coexisting substances in natural waters, the use of gamma ray irradiation for degradation of organic species can be influenced by several factors. To our knowledge, the factors that affect the degradation of diclofenac by gamma ray irradiation have not yet been studied. In the current study, the main objectives are: (a) to assess the factors that affect the degradation efficiency of diclofenac, such as the initial concentration, initial pH, and the concentration of the additives such as H2O2 (OH radical promoter), CH3OH (OH radical scavenger), thiourea (OH, H, and eaq scavenger), humic acid (HA), and NO3 (coexisting substances in natural waters); and (b) to propose possible intermediate products and the corresponding transformation pathways.

2.2 Experimental procedures Gamma rays were obtained from a 60Co source (1.85 1016 Bq) (Institute of Atomic Energy, Jiangsu Academy of Agriculture Sciences, China). Degradation experiments were performed in a 50-mL airtight Pyrex bottle loaded with 25 mL of diclofenac solutions at different initial concentrations of 20.5, 30.4, and 50.1 mg L1. All solutions were allowed to reach equilibrium under atmospheric pressure and room temperature before irradiation and were sealed with screw caps to prevent the introduction of air. The radiation doses were controlled at 0, 0.3, 0.5, 0.7, and 1.0 kGy by changing the distance between the reactor and the gamma ray source. The silver dichromate dosimeters prepared following the American Society for Testing and Materials standards were used to measure the dose absorbed by the samples. The effects of pH conditions and additives such as H2O2, CH3OH, thiourea, HA, and NO3 on the degradation were also investigated. Typically, the initial concentration of diclofenac was controlled at 30.4 mg L1, and the pH conditions of the solutions were adjusted using HCl (0.01 M) and NaOH (0.01 M) solutions. 2.3 Analysis 2.3.1 Analysis of diclofenac The concentration of diclofenac was determined using an Agilent 1200 series HPLC system equipped with a multiwavelength UV diode array detector. An Agilent Hypersil ODS column (2504.6 mm i.d., 5 m) was employed for the separation, and the column temperature was 30C. The mobile phase consisted of methanol and 4% aqueous acetic acid (80/20, v/v) with a flow rate of 1.0 mL min1. The detection wavelength for diclofenac was 276 nm. Typically, the retention time of diclofenac was 5.61 min under these conditions. Calibration was conducted daily, and R2 was ensured to be greater than 0.99 in all the cases. All experiments were repeated twice, and the average values were used. The experimental errors were below 5%. Total organic carbon (TOC) was determined with a TOC analyzer (Shimadzu, TOC-5000A). Calibration was achieved by injecting standards of potassium phthalate. The pH was measured via pH monitor (Shanghai Kangyi Instrument Co., Ltd. China, PHS-2C). 2.3.2 Identification of degradation products

2 Materials and methods 2.1 Chemicals and reagents The diclofenac (2-[2,6-(dichlorophenyl) amino] phenylacetic acid) standard and methanol (HPLC grade, 99.9%) were purchased from Sigma-Aldrich. HCl, NaOH, NaNO3, H2O2, CH3OH, thiourea, and HA were all commercially obtained in an analytical grade. The identification of diclofenac and its degradation products was characterized by LC-MS (ThermoQuestLCQ Duo, USA) with Beta Basic-C18 HPLC column (1502.1 mm i.d., 5 m; Finnigan, Thermo, USA). The mobile phase was a degassed mixture of methanol and 0.5% aqueous acetic acid (80/20, v/v) with a flow rate of 1.0 mL min1. The sample injection volume

Environ Sci Pollut Res (2011) 18:12431252

100 10.0 5.00

1245

C
80

TOC

8.0

4.00

pH
(%)
60

6.0

3.00

40

4.0

2.00

20

2.0

1.00

0 0.0 0.2 0.4 0.6 0.8 1.0

0.0

0.00

G (molecules (100 eV) )

was 20 L. Other operating parameters of the LC were the same as what were used in the analysis of diclofenac using the HPLC system. MS conditions were as follows: The electrospray ionization interface was selected. The capillary temperature was 275C with a voltage of 16 V. The spray voltage was 5000 V, and the sheath gas flow rate was 18 arb. The spectra were acquired in negative scan mode over the 50600 m/z range. Typically, the retention time of diclofenac was 3.79 min. 3 Results and discussion 3.1 Degradation of diclofenac by gamma ray irradiation The amount of diclofenac reduced from per unit dose, i.e., specific reduction efficiency [G value, molecules
100

Radiation dose (kGy)

Fig. 1 Changes of degradation efficiency (C), removal rate (TOC), solution pH, and G value in the gamma ray-irradiated diclofenac degradation process

(%)

40

Co= 20.5 mg L Co= 30.4 mg L Co= 50.1 mg L

-1 -1 -1

(%)

Fig. 2 Impacts of various factors on the diclofenac degradation efficiency by gamma ray irradiation: a initial concentration, b H2O2, c CH3OH, d thiourea, e humic acid, and f NO3

100

pH

-1

(a)
80 80

(b)

60

60

40

20

20

0 0.0 0.2 0.4 0.6 0.8 1.0

0 0 2 4 6 8 10 12

Radiation dose (kGy)

100 100

Concentration of H2O2 (%)

(c)
80 80

(d)

60
(%)

60
1.5% CH3OH
(%)

Blank 3.0% CH3OH

40

40

20

20

Blank 0.28 mM thiourea 0.56 mM thiourea

0 0.0 0.2 0.4 0.6 0.8 1.0

0 0.0 0.2 0.4 0.6 0.8 1.0

Radiation dose (kGy)

100 100

Radiation dose (kGy)

(e)
80

(f)
80

60
(%) (%)

60
Blank 0.28 mM NO3 0.56 mM NO3
-

40

40

20

20

0
0 40 80

0 0.0 0.2 0.4 0.6 0.8 1.0

Concentration of humic acid (mg-1L)

Radiation dose (kGy)

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(a)

(b)
SLFSN-MS-MS #146-174 RT: 3.48-4.05 AV: 5 NL: 2.21E3 F: - c ESI Full ms2 250.11@40.00 [ 65.00-252.00] 100 80 60 40 20 0 80 100 120 140 160 180 200 220 240 214.0

Relative Abundance

m/z

(c)
SLFSN-MS-MS #145-173 RT: 3.50-4.07 AV: 5 NL: 7.62E4 F: - c ESI Full ms2 293.83@40.00 [ 80.00-295.00] 100 250.0

Relative Abundance

80 60 40 20 0 80 100 120 140 160 180 200 220 240 260 280

m/z

Fig. 3 ESI mass spectra of diclofenac. MS spectrum (a), MS2 spectrum of m/z 250 (b), m/z 294 (c), m/z 296 (d), m/z 310 (e), and m/z 312 (f) (initial concentration=30.4 mg L1, initial pH 6.31, radiation dose=0.7 kGy)

Environ Sci Pollut Res (2011) 18:12431252

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(d)
SLFSN-MS-MS #146-174 RT: 3.52-4.09 AV: 5 NL: 5.38E4 F: - c ESI Full ms2 295.82@40.00 [ 80.00-297.00]

100

252.0

Relative Abundance

80 60 40
251.1

20 0 80 100 120 140 160 180 200 220

250.2

240

260

280

m/z

(e)
SLFSN-MS-MS #85-121 RT: 2.10-2.82 AV: 6 NL: 1.74E4 F: - c ESI Full ms2 309.81@40.00 [ 85.00-311.00] 100 265.9

Relative Abundance

80 60 40 229.9 20 194.1 0 100 120 140 160 180 200 220 240 263.6 260 280

m/z

(f)
SLFSN-MS-MS #92-116 RT: 2.27-2.70 AV: 4 NL: 1.53E4 F: - c ESI Full ms2 311.83@40.00 [ 85.00-313.00] 100 80 60 40 229.8 20 231.9 194.2 0 100 120 140 160 180 200 220 240 260 280 225.8 266.9 268.0

Relative Abundance

m/z

Fig. 3 (continued)

(100 eV)1], can be calculated according to Eq. 1 (Junko 1997): G $RNA =D 6:24 1019 1

The degradation efficiency (C, in percent) or removal rate (TOC, in percent) of diclofenac was defined in Eq. 2: h Co Ct=Co 100% 2

where R is the amount of reduced diclofenac (M), NA is Avogadro's constant (6.021023 molecules mol1), D is the radiation dose (102 kGy), and 6.241019 is the conversion constant from kilogray to 100 eV L1 (100 eV L1 kGy1).

where Ct is the residual diclofenac concentration or TOC of diclofenac (milligrams per liter) after gamma ray irradiation and Co is the initial diclofenac concentration or TOC of diclofenac (milligrams per liter).

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Figure 1 shows the changes of C, TOC, solution pH, and G value in the gamma ray-irradiated diclofenac degradation process. The results showed that with accumulating radiation dose from 0.3 to 1.0 kGy, pH decreased from 5.16 to 4.47. The degradation efficiency steadily increased from 57% to 89.2%, whereas the removal rate of TOC was notably lower. In addition, the G values decreased from 1.89 molecules(100 eV)1 at the dose of 0.3 kGy to 0.89 molecules(100 eV)1 at the dose of 1.0 kGy. The possible reason for the decrease in G value was that although the radical species, including OH, H, and eaq, increased at higher radiation doses, radicalradical recombination reactions also increased, which would decrease the reaction activity. 3.2 Factors affecting the degradation of diclofenac 3.2.1 Effect of initial concentration

solution pH from 11.19 to 6.31 was found to increase the degradation efficiency of diclofenac from 62.9% to 75.6% at 0.7 kGy. Further decreasing the solution pH to 2.59 enhanced the degradation efficiency to 85.0%. The degradation efficiency was higher under acidic conditions than under neutral and alkaline media. Through gamma ray irradiation, freed electrons are generated in the solution, which react with H+ ions to produce H radicals. Subsequently, H radicals react with O2 and other molecules to produce OH radicals. In alkaline solutions, however, H readily reacts with OH to generate eaq, which enhances the probability of recombination between OH and eaq, and subsequently reduces the effective radical concentration. As a result, the concentration of OH radicals is higher in acidic conditions than in alkaline conditions, and thus accelerates the reaction of OH with diclofenac molecules. 3.2.3 Effect of H2O2 as additive

An exponential relationship can be used to describe the relationship between residual concentration and radiation doses, as shown in Eq. 3 (Nickelsen et al. 1994): RD Ro expkD 3

RD is the residual diclofenac concentration at any radiation dose (milligrams per liter), D is the radiation dose (kilogray), Ro is the initial concentration of diclofenac (milligrams per liter), and k is the kinetics constant (per kilogray). Figure 2a compares the degradation efficiency of diclofenac at three initial concentrations of 20.5, 30.4, and 50.1 mg L 1 . As seen from the figure, the degradation efficiency decreased with the increase of the initial concentration. At three initial concentrations, the kinetics constants were 2.55, 2.12, and 1.90 kGy 1 and the G values were 0.62, 0.89, and 1.40 molecules (100 eV) 1, respectively, at a radiation dose of 1 kGy. Using Eq. 3, the required radiation doses to reduce the initial concentration by 90% were estimated to be 0.9, 1.1, and 1.2 kGy, respectively. The fact that G values increased with increasing initial concentrations indicated that reactive radicals produced by water radiolysis at higher concentrations had a greater opportunity to react with the molecules, leading to higher removal quantities. 3.2.2 Effect of initial pH The pH of the solution is always an important parameter that affects the degradation of pollutants. The degradation of diclofenac by gamma ray irradiation was studied in pH ranging from 11.19 to 2.59. The decrease in

Figure 2b shows the degradation efficiency of diclofenac under various H2O2 concentrations at 0.7 kGy of radiation dose. H2O2 is a common source of OH radicals. When H2O2 was added as a radical promoter at appropriate concentrations, H2O2 accelerated degradation by generating additional OH. However, when the concentration of H2O2 exceeds the optimal concentration, H2O2 reacts with OH to form a much weaker radical (HO2) (Irmak et al. 2006; Flox et al. 2006), resulting in decreased degradation efficiency. 3.2.4 Effect of CH3OH and thiourea as additives The effect of CH3OH and thiourea as radical scavengers on the degradation of diclofenac was investigated under different radiation doses, and the results are illustrated in Fig. 2c, d. With the addition of CH3OH and thiourea, the degradation efficiency of diclofenac was retarded significantly; both were lower than that in the absence of the additives. Since CH3OH is the OH radical scavenger and thiourea is the scavenger of OH, H, and eaq, the results indicated that degradation of diclofenac takes place via two pathways: oxidation by OH radicals and reduction by eaq and H. 3.2.5 Effect of HA and NO3 as additives The degradation efficiency of organic species under gamma ray irradiation is often influenced by coexisting substances in natural waters. Figure 2e shows the degradation efficiency of diclofenac under various HA concentrations at the radiation dose of 0.7 kGy. The results showed that the degradation efficiency was higher in the presence of HA

Environ Sci Pollut Res (2011) 18:12431252

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than that in the absence of them. These results might be caused by the fact that HA exposed to gamma ray irradiation forms the excited triplet states (3HA*), which generates various reactive oxidation species, including OH radicals, singlet oxygen (1O2), and H2O2 (Eqs. 4, 5, and 6) (Sandvik et al. 2000; Zhan et al. 2006). HA hv1 HA ! 3 HA

Eq. 11 represent the amount of the produced radicals per 100 eV of energy. H 2 O ! e aq 2:6 H 0:55 OH2:7 H2 0:45 H2 O2 0:71 H3 O 2:6 11

HA O2 1 O2 HA HA O2 HO2 O2 OH HA

The effect of NO3 as an additive on the degradation of diclofenac was also investigated under different radiation doses, and the results are illustrated in Fig. 2f. NO3 slightly affected the degradation efficiency. Further analysis revealed that the kinetics constants were 2.12, 2.51, and 2.43 kGy1, when 0, 0.28, and 0.56 mM of NO3 were added, respectively. In fact, the addition of NO3 leads to the formation of hydrated electrons eaq and is also a primary source of OH and NO2 radicals (Eqs. 7, 8, and 9) (Brezonik and Fulkerson-Brekken 1998). However, excessive addition of NO3 clears eaq through Eq. 10 and ultimately decreases the degradation efficiency of diclofenac (Singh and Kremers 2002). NO 3 hv NO3 NO 3 NO3
NO 2 O NO2 eaq O

7 8

Different AOPs aimed at pollutant oxidation lead to different end products. Although with some similarities, the reaction pathways in these methods also differ from each other (Poiger et al. 2001; Vogna et al. 2004; Lenidas et al. 2005). Hence, diclofenac follows different reaction pathways depending on the degradation treatment. The current study was focused mainly on the transformation pathways of diclofenac and particular attention was given to the identification of the degradation products. The intermediate products were identified by their chromatographic behavior and kinetics of evolution, coupled with accurate analyses of the MS and MS2 spectra. Figure 3 shows the ESI mass spectra of the diclofenac solution by gamma ray irradiation. Figure 4 illustrates the possible reaction mechanisms between OH, eaq, H, and diclofenac. Based on the identification of intermediate products, the corresponding transformation pathways are proposed in Fig. 5. Based on the analysis of LC-MS, the presence of chlorine and its characteristic isotopic species (35Cl and 37Cl) in diclofenac can be used to identify the corresponding degradation products. As shown in Fig. 5a, the isotopic peaks at M, M + 2, and M + 4 with relative intensities at the ratio of 9:6:1, are characteristics of the presence of two chlorine atoms as observed in the deprotonated diclofenac ([MH]) mass spectrum (ions 294/296/298). CollisionH2C H N Cl Cl CH2
N

Cl

NO2 O H2 O NO2 OH OH 9
CH3 H N Cl Cl

OH. OH.
CH2COOH H N Cl

OH. OH.
HO COOH CHOH H N Cl Cl

CH2COOH H N Cl

Cl

e aq

NO 3

NO 2

NO2 3

2 NO2

10
OH.
CH2COOH Cl N O Cl

Cl

In conclusion, the extensive coexisting substances in natural waters, such as HA and NO3, would not affect the degradation efficiency of diclofenac by gamma ray irradiation. 3.3 Identification of possible degradation products and transformation pathways During gamma ray irradiation, water radiolysis happened within about 107 s. Three reactive species, namely, H, eaq, and OH, as well as the less reactive species H3O+ were produced (Eq. 11). The numbers (in parenthesis) in

CHO H N

Cl e aq-

CHO H N .

Cl

CHO

Cl H N

H.

Cl

Fig. 4 Possible reaction mechanisms between OH, eaq, H, and diclofenac

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(a)

CH2COOH Cl H N

m/z=294/296/298
Cl

H2 C

H N

Cl

CH3

H N Cl

Cl

CH2 N Cl

Cl

Cl

m/z=250/252

H 2C

H N

Cl

CH3

H N

Cl

CH2 N

Cl

m/z=214/216

CH2COOH

Cl

(b)

H N

m/z=294/296/298
Cl

CH2COOH H N

Cl

CH2COOH H N

Cl

CH2COOH H N

Cl CH2COOH N Cl

COOH CHOH H N Cl

Cl

OH

Cl OH

HO

Cl O Cl Cl

m/z=310/312/314

H2C

H N

Cl

CH3 H N

Cl

CH2
N

Cl

CH3 N HO Cl O Cl

Cl CHO
H N Cl

HO

Cl

HO

Cl

m/z=266/268/270
Cl

H2C

H N

Cl

CH3 H N

Cl

CH2
N

Cl

CH3 N

Cl
CHO H N Cl

HO

HO

HO O

m/z=230/232

H2C

H N

CH3 H N

CH2
N

CH3 N

CHO H N

m/z=194

HO

HO

HO O

Fig. 5 Proposed pathways of diclofenac transformation induced by gamma ray irradiation

induced dissociation of m/z 294 shows the loss of carboxyl (dehydration and the subsequent loss of a neutral CO) to produce the fragment ion with m/z 250, which was followed by subsequent loss of chloride ion forming m/z 214. As shown in Fig. 5b, the compounds holding m/z 310/ 312/314 are probably produced through an OH radical

attack, leading to the hydroxylation of the molecule. The formation of several species with the same m/z ratio is due to the non-selectivity of the OH radical attack (Strukul 1992). Among the five m/z 310/312 degradations, one is due to an attack on the lateral chain, whereas the others should bear an OH group on the aromatic ring. Some

Environ Sci Pollut Res (2011) 18:12431252

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peculiar losses were present: (1) The first, the second, and the third degradation products yielded an accurate mass m/z of 312, which gave the best-fit formula C14H11NO3Cl2 (neutral molecule). This formula corresponds to the addition of one oxygen atom, which is consistent with the formation of monohydroxylated derivatives. The fragmentation shows [MH] ions with m/z 310, 312, and 314 at a ratio of 9:6:1 and again the loss of carboxyl to form m/z 266, 268, and 270; this was followed by two subsequent losses of chloride ions, resulting in m/z 230/232 and m/z 194. The fourth degradation product showed an accurate mass of m/z 310, which fits the formula C14H9NO3Cl2 (neutral molecule), corresponding to one more oxygen atom and two less hydrogen atoms than diclofenac. The presence of this compounds suggests that the initial degradation of diclofenac was due to the attack by OH radicals on the aromatic ring, yielding a keto-derivative, which is further oxidized into the corresponding quinone imine derivative. The degradation step in the quinone imine derivative was decarboxylation of the phenylacetic acid group to C13H9NOCl2. (2) The fifth m/z 310/312 degradation was due to an attack on the lateral chain. The fragment at m/z 266/268 was due to the loss of the formic acid from m/z 310/312, whereas the fragments at m/z 230/232 and 194 were through subsequent losses of two chloride ions.

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4 Conclusions Study results suggest that gamma ray irradiation has been shown to be an effective way to degrade diclofenac. The degradation efficiency of diclofenac increased significantly with the increase of radiation dose. Detailed examination of the diclofenac degradation performances showed that: (1) Diclofenac degradation efficiency decreased with the increase in its initial concentration. (2) Diclofenac degradation efficiency is higher under acidic conditions than in neutral and alkaline media. (3) Study results with three additives (H2O2, CH3OH, and thiourea) indicated that the degradation of diclofenac takes place via two pathways, oxidation by HO radicals and reduction by eaq and H. (4) The extensive coexisting substances in natural waters, such as HA and NO3, do not affect the degradation efficiency significantly. Based on the identified intermediate products, it is suggested that the transformation pathways are mainly initiated by hydrogen atoms H, hydrated electrons eaq, and hydroxyl radicals OH.

Acknowledgments Zheng Zheng gratefully acknowledges support from the Natural Science Foundation of China (Foundation item No. 10475040). We would like to thank Zhao YongFu for his help in the experimental work.

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