Chemical Engineering Journal 243 (2014) 713

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Chemical Engineering Journal

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Ballast water treatment using UV/TiO2 advanced oxidation processes: An approach to invasive species prevention
Nahui Zhang a, Kefeng Hu b,, Baohua Shan c
a

Marine Engineering, Dalian Maritime University, 1 Linghai Road, Dalian, Liaoning 116026, China China Classication Society, 9 Dongzhimen Nan Da Jie, Beijing 100007, China c Ahead Ocean Technology Co., Ltd., 6 Caishi Street, Dalian, Liaoning 116026, China
b

h i g h l i g h t s
 We investigated the UV/TiO2 process for ballast water treatment.  UV/TiO2 treatment had the potential to inhibit plankton regrowth.  The advantages of UV/TiO2 at low UV dose (i.e., 75%) were much greater.  The concentrations of disinfection by-products formed during UV/TiO2 treatment were very low.

a r t i c l e

i n f o

a b s t r a c t
Spread of marine invasive species (MIS) via ships ballast water causes global biotic homogenization and extinctions. In this study, a UV/TiO2 ballast water treatment system (BWTS) was designed to reduce transport of MIS. UV dose proles simulated by computational uid dynamics indicated that, depending on the ow rate and UV light intensity, the average applied UV dose was 260 mJ/cm2. Combined UV/TiO2 treatment produced excess hydroxyl radicals that were conrmed by high performance liquid chromatography using a trapping agent. We then compared the effectiveness of UV/TiO2 BWTS against UV-alone BWTS at two different UV doses (i.e., 100% and 75%). We found that, even though UV alone reduced the abundance of all tested organisms, UV/TiO2 signicantly reduced the abundance of all groups and led to a greater reduction than UV alone. Each trial should include the storage of treated ballast water for at least 120 h according to Guideline G8 of the International Maritime Organization. Comparison tests after 120 h of storage period showed that the plankton densities of treated water for UV/TiO2 treatment in the P50 lm group further deceased from 4 to 2 individuals (ind.)/m3, whereas those for UV-alone treatment increased from 6 to 57 ind./m3, revealing that UV/TiO2 treatment had the potential to inhibit plankton regrowth, but UV alone did not. Although the efcacy of both strategies increased after 120 h of storage period, the densities of microbes in discharge samples from the UV/TiO2 treatment were signicantly lower than those in samples from UV-alone treatment. Moreover, the advantages of UV/TiO2 at low UV dose (i.e., 75%) were much greater and the concentrations of disinfection by-products (e.g., trihalomethanes, haloacetic acids) were observed in levels of 0.011 lg/L. 2014 Elsevier B.V. All rights reserved.

Article history: Received 10 September 2013 Received in revised form 24 December 2013 Accepted 26 December 2013 Available online 4 January 2014 Keywords: Ballast water UV/TiO2 process Disinfection by-products Hydroxyl radicals

1. Introduction Ballast water is absolutely essential to the safe and efcient operation of modern shipping, providing balance and stability to un-laden ships. Annually over 10 billion tons of ballast water are transferred among ports [1]. An estimated 7000 marine and coastal species travel across the worlds oceans every day in ballast tanks and 84% of the worlds 232 marine ecoregions have reported ndings of invasive species [2]. The introduction of marine invasive
Corresponding author. Tel.: +86 10 58112456; fax: +86 10 58112842.
E-mail address: hukf@ccs.org.cn (K. Hu). 1385-8947/$ - see front matter 2014 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.cej.2013.12.082

species (MIS) into new environments is regarded as one of four major risks to global marine environmental safety [3], and ballast water discharge has been identied as a leading vector for MIS [47]. To minimize the associated impacts on health, environment and economy, the International Maritime Organization (IMO) adopted the International Convention for the Control and Management of Ships Ballast Water and Sediments in 2004 [8]. It will enter into force 12 months after the date on which 30 countries representing 35% of the gross tonnage of the worlds merchant shipping have ratied it. To date, a total of 37 countries representing 29% of the worlds merchant tonnage have signed [9]. In the near future, the

N. Zhang et al. / Chemical Engineering Journal 243 (2014) 713

maximum concentrations of living organisms that can be released with ballast water must not exceed D-2 discharge standards of the IMO: ships shall discharge (1) less than 10 viable organisms P50 lm per m3; (2) less than 10 viable organisms P10 to <50 lm per mL; (3) less than 1 colony forming unit (cfu) of toxicogenic Vibrio cholerae (O1 and O139) per 100 mL; less than 250 cfu of Escherichia coli per 100 mL; and less than 100 cfu of intestinal Enterococci per 100 mL [8]. An efcient way to achieve this aim is the physical and/or chemical treatment of ballast water on board [7]. To prevent the introduction of MIS via ships ballast water, different treatment methods have been proposed, such as electrolysis, ultraviolet (UV) radiation, chemical methods (e.g., chlorine, ozone, calcium hypochlorite, peracetic acid, acetic acid). Each of the methods mentioned above has its own advantages and disadvantages. For example, electrolysis and chemical treatment are considered to be effective but they also cause corrosion of ballast tanks, introduce hazardous chemicals, and generate undesirable by-products [10]. UV radiation is physical treatment with no chemical doses, but its disinfection efciencies are claimed limited [1113]. In addition, UV exposure is usually done at both intake and discharge of ballast water, due to its low ability to inhibit microorganisms reproduction and its effectiveness degrades with cloudy or turbid water that restricts UV light penetration [14]. Therefore, the development of more effective and environmentally friendly treatment technologies has become an urgent issue. Recently, UV-based advanced oxidation processes (AOP) (e.g., UV/TiO2, UV/AgTiO2/O3, UV/H2O2) have been investigated for their treatment efcacy [1518]. UV radiation combined with TiO2 leads to an AOP with improved oxidative properties due to the in situ formation of hydroxyl radicals (OH). The mechanism of OH formation is described as follows: (1) irradiation with photons that have their energy greater than the bandgap energy, generally leads to the formation of an electron/hole pair in TiO2 particle (Eq. (1)) [19,20]; (2) valence band holes (hv b ) have been shown to be powerful oxidants, whereas conduction band electrons (e cb ) can act as reductants. The holes in the valence band can react with surface-bound water and hydroxide groups to give OH (Eqs. (2) and (3)) [20]; and (3) the electron can be transferred to the dissolved oxygen to give superoxide radical anion (O2 ) (Eq. (4)) [20]. O2 and its protonated form subsequently dismutate to yield hydrogen peroxide (H2O2) or peroxide anion (Eq. (5)). The photocatalytic reduction of H2O2 by e cb then leads to the production of next OH (Eq. (6)) [21,22].

may exist within the reactor. On the other hand, the further oxidation by OH of bromide in seawater would lead to the formation of hypobromous acid (HOBr) that is generally quantied as total residual oxidant (TRO) and presents a real interest for disinfection as they could inhibit bacterial regrowth after treatment [23]. If OH is formed, brominated organic compounds (e.g., bromate, tribromomethane, tribromoacetic acid) can arise from bromide as mentioned above. In this study, the effectiveness of a laboratory-based ballast water treatment systems (BWTS) using UV/TiO2 technology were evaluated in the inactivation of MIS via ballast water, by comparing the effectiveness of UV/TiO2 versus UV alone. UV dose was calculated using a computational uid dynamics (CFD) model. In order to conrm the assumption presented in the introduction above, OH measurement and bromide oxidation products by quantication of TRO, bromate, trihalomethanes (THMs), haloacetonitriles (HANs) and haloacetic acids (HAAs) were also monitored. 2. Materials and methods 2.1. Test facility and experimental design Natural seawater used as inuent water was supplied from Dalian Harbor in the Yellow Sea, China, and was kept in the holding tank (Fig. 1). Salinity, temperature and pH of inuent water were 32.5 PSU, 23.4 C and 8.15, respectively. Plankton densities were adjusted by adding concentrated natural populations from the harbor into the inuent water; the target densities for organisms P50 lm and P10 to <50 lm were at least 105 individuals (ind.)/ m3 and 103 cells/mL, respectively [24]. To determine if a UV/TiO2-based BWTS more effectively reduces the introduction of MIS via ballast water than a UV-alone BWTS, we conducted two comparison trials. The only difference between tested systems was that one utilized UV-alone treatment, while the other utilized an AOP technology involving UV plus a TiO2 nanothin lm. UV-alone treatment was conducted in a cylindrical reactor with a 200 mm inner diameter and a height of 390 mm. Five natural quartz sleeves holding ve low pressure (LP) UV lamps with power of 600 W (Beasun Electronic Co., Ltd., Beijing, China) were placed at the center of reactor. UV/TiO2 treatment was carried out in the same UV reactor with a TiO2 nanothin lm encircling the UV lamps. Two paired trials corresponding operating conditions of UV alone and UV/TiO2 were conducted. For each trial, the inuent water directed to tank 1 was treated by UV irradiation alone, whereas that directed to tank 2 was treated with UV/TiO2 (Fig. 1) and the effectiveness of the two different BWTS on organism densities was measured. According to Guideline G8 of the IMO, each trial should include the storage of treated ballast water for at least 120 h. Therefore, treated water was stored in tanks for 120 h, after which the UV/TiO2 tank was discharged directly and the UV-alone tank was subjected to another round of UV radiation treatment and then discharged. 2.2. UV dose determination and adjustion

TiO2 hv ! hv b e cb H2 O hv b ! OH H OH hv b ! OH
O2 e cb ! O2

1 2 3 4 5 6

2O2 2H $ 2HO2 ! H2 O2 O2
H2 O2 e cb ! OH OH

For disinfection purposes, especially ballast water treatment processes, it is necessary to monitor and control the applied dose of active substances that has a general or specic action on or against harmful aquatic organisms and pathogens. There are two inactivation mechanisms for UV/TiO2 treatment, one is UV radiation, the other is OH produced from photocatalytic reaction. For practical UV disinfection devices, the characterization of UV radiation prole is important, since UV radiation does not spread homogenously in water and zones where the radiation is weaker

Disinfection level and operation cost are determined directly by UV reactor geometry conguration [25]. UV dose is determined by both incident radiation and exposure time in UV reactor (Eq. (7)).

UV dose mJ=cm2 incident radiation mW=cm2 exposure time s 7

Since it is impractical and cost-ineffective to apply bioassay tests to evaluate the performance of large-scale UV reactors, CFD coupled with irradiation model simulation was used to simulate

N. Zhang et al. / Chemical Engineering Journal 243 (2014) 713

Treated water

Discharge
Influent water

UV UV reactor reactor S.P.2, T Tank 1 S.P.4, T120h S.P.5, T120h 0h Filter

Dm Treated water Diso Flow

Holding S.P.1 tank

Discharge UV/TiO2 Tank 2 reactor S.P.3, T0h S.P.6, T120h

Sample

Magnification of sampling point

Fig. 1. Schematic representation of experimental design comparing effectiveness of ballast water treatment system (BWTS) using UV/TiO2 versus UV alone. S.P.1S.P.6 denote sampling points. T0 h and T120 h represent time scale from hour 0 to hour 120. Diso and Dm are the diameters of the sampling point opening and the main ow in the line, respectively.

movement of organisms through the UV reactor, calculate their exposure time to UV light, and compute UV dose received by various sections of the population of organisms. Fig. 2 shows the UV dose calculated by CFD model, and UV dose used in this study was 260 mJ/cm2. The CFD model was applied to design and optimize the UV reactor geometry conguration before the test. UV intensity was measured with a UV irradiance meter (Linshang Technology Co., Ltd., Shenzhen, China) during the test. Without changing ow rate, electrical ballasts (Beasun Electronic Co., Ltd., Beijing, China) were always applied to adjust the power of LP UV lamps and further to change UV intensity.

2.3. Sample collection, identication and quantication of plankton and bacteria Six sampling points (S.P.1S.P.6) and a diagram of the sampling points installed in a pipe are shown in Fig. 1. Samples for the inuent water were collected from S.P.1, while samples immediately after treatment (T0 h) were collected from S.P.2 and S.P.3 for the UV-alone and UV/TiO2, respectively. Samples for UV/TiO2 after 120 h of storage were collected from S.P.6 (T120 h), while samples for before and after UV-alone re-treatment were collected from S.P.4 and S.P.5 (T120 h), respectively. Since the capacity of BWTS is 20 m3/h, the total time needed for one test cycle was 30 min. Therefore, triplicate samples were collected at a sequence of beginning T5 (5 min), middle T15 (15 min), and end T25 (25 min). For analysis of organisms P50 lm in size, triplicate (i.e., T5, T15 and T25) 20 L samples were collected from S.P.1 for inuent water, while triplicate 1 m3 samples were collected from and S.P.2 and S.P.3 for treated water immediately after treatment (T0 h), from S.P.4, S.P.5 and S.P.6 at treated water discharge sampling event (T120 h), respectively. Water samples were concentrated through plankton net with a mesh size of 50 lm (diagonal dimension) into 60 mL specimen bottle. Five drops of stain stock solution added into specimen bottle for 30 min staining, and formalin solution added to x the samples. Then retained organisms were enumerated using total count method under a biological microscope (Olympus BX61, Tokyo, Japan) at 40100 magnication [26]. For analysis of organisms P10 to <50 lm in size, triplicate 1 L samples were collected from S.P.1, while triplicate 10 L samples were collected from S.P.2 and S.P.3 for treated water immediately after treatment (T0 h), from S.P.4, S.P.5 and S.P.6 at treated water discharge sampling event (T120 h), respectively. One and 10 L water samples were concentrated through plankton net with a mesh size of 10 lm (diagonal dimension) into 25 and 60 mL specimen bottle, respectively. Five drops of stain stock solution added into specimen bottle for 15 min staining, and formalin solution added to x the samples. The pretreated samples were left to settle for 24 h, and supernatants were extracted and transferred to a 50 mL sample container. Shacked the subsample enough before transferring a certain amount to a counting chamber with cover glass for observation using a microscopic counting under a biological microscope (Olympus BX61, Tokyo, Japan) at 200 magnication [26]. Further, 0.7 L water samples were collected in triplicate at each sampling event for microbial analysis. Heterotrophic bacteria were enumerated using the agar spread plate method with autoclaved marine broth 2216E. The culture dishes were then closed and placed upside down in a 37 0.5 C incubator for 48 h [26,27]. Escherichia coli were cultivated in an incubator at 44 0.5 C for

Fig. 2. UV dose simulated by CFD model.

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300 250 200 150

Absorbance (mAU)

24 h, and intestinal Enterococci were cultivated at temperature of 35 2 C and incubated for 24 h. E. coli and intestinal Enterococci were check using standard most probable number (MPN) protocols [26,28]. Total Vibrio sp. was determined by placing the lter on TCBS cholera medium agar plates which were incubated at 37 C for 18 h. Physiological and biochemical test kits (API 20E) were used for further identication [26]. 2.4. Chemical analysis Three replicated of 5 L water samples were collected at each sampling event for chemical analysis. A Waters high performance liquid chromatography (HPLC) (Waters Corp. Milford, MA, USA) equipped with a 2998 photodiode array detector and a Nova-Pack C18 column (5 lm, 250 4.6 mm I.D.), was employed indirectly to detect OH after a trapping reaction with 4-hydroxybenzoic acid (4-HBA). Through the determination of hydroxylated derivatives of 4-HBA, 3,4-dihydroxybenzoic acid (3,4-DHBA), the concentration of OH was evaluated relatively [29]. Detection was at 210 nm with a mobile phase composed of a 0.01 M HPLC grade phosphoric acid:HPLC grade methanol mixture (80:20 in volume) at a ow rate of 1 mL/min. Bromate was analyzed by ion chromatographic method using a ion chromatograph system (DIONEX ICS-1500, Thermo Fisher Scientic Inc., USA) following US EPA method 317.0 [30]. THMs, HANs and HAAs were analyzed according to US EPA methods 551.1 and 552.3, using a gas chromatograph (GC) with electron capture detection (Agilent 7890A, Agilent Technologies Inc., USA) [31,32]. Injections of 2 lL samples were introduced via split/splitless injector onto a GC column (HP-5MS, 30 m 0.25 mm I.D. with 0.25 lm lm thickness, J&W Scientic Agilent). Additionally, salinity, pH, temperature, dissolved oxygen and oxidation reduction potential (ORP) were measured by an YSI Multiparameter Water Quality Sonde (YSI-6600 V2, Yellow Springs, OH, USA). Total suspended solid (TSS) was measured by a gravimetric method [33]. Total organic carbon (TOC) was processed following US EPA method 415.3 [34]. TRO was determined by a colorimetric N,N-diethyl-p-phenylenediamine method based on US EPA method 330.5 [35]. 3. Results and discussion 3.1. OH characterization
OH is known to cause damage to protein, lipid, DNA and RNA, leading to tissue injury and cell death [36]. Measurement of OH formation is thus essential to conrm its existence and understand its role involved in organisms inactivation process. While it is known that measurement of OH is very difcult due to its high reactivity and low abundance in aqueous solution. In this study, 4-HBA that has proven to overcome some of the difculties inherent to salicylate was used as OH trapping agent [29], and HPLC was then employed to characterize OH indirectly by determining its single reaction products with 4-HBA, 3,4-DHBA. To conrm OH existence during UV/TiO2 treatment process, an additional experiment was carried out at laboratory. Using the same UV dose, 3,4-DHBA formation from the UV/TiO2 treatment process was compared to its formation from the UV irradiation alone. The characteristic one peak of 3,4-DHBA was clearly observed upon HPLC chromatogram after UV/TiO2 treatment (Fig. 3b), indicating that OH was really generated on the surface of TiO2 membrane under UV radiation. In contrast, no 3,4-DHBA peak were signicantly detected after UV radiation alone (Fig. 3a). In addition, the change of peak height of 3,4-DHBA at different UV doses is also shown in Fig. 3b. There is no signicantly

(a)

UV treatment alone UV dose = 260 mJ/cm2

4-HBA

100 50 0 300 250 200 150 100 50

B

3,4-DHBA

(b)

UV/TiO2 treatment A: UV dose = 260 mJ/cm2 B: UV dose = 221 mJ/cm2 C: UV dose = 195 mJ/cm2

4-HBA

3,4-DHBA
C A

0 10 12 14 16 18 20 22 24

Retention Time (min)

Fig. 3. HPLC chromatograms of 4-HBA and 3,4-DHBA: (a) UV radiation alone, and (b) UV/TiO2 treatment. Mobile phase consisting of 20% (v/v) methanol and 80% (v/v) 0.01 M phosphoric acid was used to separate 3,4-DHBA.

difference in peak height of 3,4-DHBA, indicating the amount of produced OH is not changed with the present applied UV doses, which is consistent with the results reported by Bahnemann et al. [37]. 3.2. Efciency of UV/TiO2 BWTS Initial plankton densities of inuent water in the P50 lm and P10 to <50 lm groups were 5.85 105 ind./m3 and 5000 cells/ mL, respectively. The densities of microbes were relatively high in all samples (Table 1). Two paired tests were conducted at two different UV doses (i.e., trial 1 = 100% UV dose and trial 2 = 75% UV dose). The results indicated that no Vibrio cholera or intestinal Enterococci were present in any treated water samples (Table 1). The densities of organisms in all groups were signicantly reduced immediately after UV-alone or UV/TiO2 when compared to that of initial inuent water; however, the decreases in response to UV/TiO2 were signicantly higher than those in response to UV alone (Table 1). The inactivation ratios for UV/TiO2 tests decreased by about 3-log for heterotrophic bacteria and 5-log for E. coli immediately after treatment from an initial bacterial concentration of around 106 cfu/100 mL in inuent water (Table 1). In addition, the treated water (i.e., after UV-alone and UV/TiO2 treatment) was held in the tanks 1 and 2 (Fig. 1) for 120 h to ensure that biotic factors, such as biological re-growth, DNA repair in organism and resting stages, would not develop during testing. And the effects of BWTS on organism concentration were tested by comparing the treated water to the untreated water in order to eliminate the factor of natural death causing by survival environmental conditions changes. After the storage period of 120 h, the plankton densities of untreated water (i.e., the rest of the inuent water in the holding tank) in the P50 lm and P10 to <50 lm groups were around 3.7 104 ind./m3 and 500 cells/mL (Table 1), respectively, indicating that there was no obvious reduction in untreated water when compared to initial inuent water, and the test cycle was valid as the untreated water with viable organism density exceeding 10 times the maximum permitted values of Regulation D-2.1 (i.e., greater than 100 viable organisms P50 lm per m3, and greater than 100 viable organisms P10 to <50 lm

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Table 1 Plankton densities in the P50 lm and P10 to <50 lm groups and microbes in inuent water, treated water after UV irradiation alone (T0 h and T120 h), and treated water after UV/ TiO2 treatment (T0 h and T120 h). Mean standard deviation of replicate measurements (n = 3). Sampling points Inuent water S.P.1 Trial 1 (100% UV dose) a Organisms P50 lm (ind./m3) Organisms P10 to <50 lm (cells/mL) Heterotrophic bacteria (cfu/100 mL) E. coli (MPN/100 mL) Intestinal Enterococci (cfu/100 mL) Vibrio cholera (cfu/100 mL) Trial 2 (75% UV dose) b Organisms P50 lm (ind./m3) Organisms P10 to <50 lm (cells/mL) Heterotrophic bacteria (cfu/100 mL) E. coli (MPN/100 mL) Intestinal Enterococci (cfu/100 mL) Vibrio cholera (cfu/100 mL)
a b c d

T0 h UV alone S.P.2 62 8.14 1.20 2333 321 46 3 NDc NDc 93 9.8 1.1 5700 265 256 15 NDc NDc UV/TiO2 S.P.3 42 4.07 0.12 1500 400 <2 NDc NDc 4.52 0.67 41 1733 321 61 NDc NDc

T120 h Untreated water S.P.1 37,567 551 476 57 390,000 20,000 3333 208 NDc NDc 36,500 200 524 10 410,000 26,458 3633 416 NDc NDc UV alone (before)d S.P.4 57 10 51 8 14,066 251 414 25 NDc NDc 50 8 74 10 19,600 2480 633 16 NDc NDc UV alone (after) S.P.5 72 41 3730 404 12 3 NDc NDc 83 8.82 1.10 7170 550 19 3 NDc NDc
d

UV/TiO2 S.P.6 22 0.80 0.12 9633 513 16 3 NDc NDc 2.33 0.58 2.12 0.08 10,400 2000 22 6 NDc NDc

585,333 2517 5010 76 5,266,667 208,167 3,366,667 152,753 14 3 NDc 584,667 1528 4967 40 5,233,333 208,167 3,400,000 300,000 13 1 NDc

Denotes Denotes Denotes Denotes

UV dose is 260 mJ/cm2. UV dose is 195 mJ/cm2. not detected. without and with secondary UV radiation.

per mL) according to Guideline G8 of the IMO [24]. The densities of organisms in treated water in the P50 lm and the P10 to <50 lm groups for UV/TiO2 treatment decreased further after the storage period of 120 h, whereas those for UV-alone treatment (without secondary UV radiation) increased (Table 1). These results are particularly promising given the fact that the complete inactivation was attributed to both OH treatment and UV radiation, and the possibility of organism regrowth and dark repair of DNA were reduced. In contrast, the densities of heterotrophic bacteria and E. coli with strong regrowth ability increased after 120 h of storage period, with the increases in UV-alone treatment without secondary UV radiation being signicantly higher than those in the UV/TiO2 treatment (Table 1). Similar results were observed in trial 2. In trial 2, the density of organisms in all groups immediately after UV/TiO2 at low UV dose (i.e., 75%) treatment was still far lower than that of the proposed D-2 discharge standard of the IMO, whereas the density of organisms in the UV alone almost failed to meet the performance standard. These ndings indicate that, at low UV dose, the effects of UV/TiO2 are much greater than those of UV alone (Table 1). Our ndings are very important to a real world application, as luminous decay, fouled quartz sleeves, and high turbidity and low clarity water can restrict UV light penetration, leading to reduce UV dose reaching the organism and poor performance of UV-alone or UV/TiO2 BWTS. As a result, the UV/ TiO2 treatment process may be particularly benecial when there are challenging poor water conditions at the point of ballast water uptake and/or poor working conditions for the BWTS. On the other hand, from the inactivation test results, it can be notice that after 120 h of storage period, secondary UV radiation is necessary for UV alone treatment to meet the D-2 discharge standard of the IMO [24], whereas it is not necessary for the UV/TiO2 treatment (Table 1). The energy cost was calculated from the UV lamp power (P) and treatment time (t). One assumption made was that the normal UV-alone BWTS ran on 85% rated power of UV lamp to effectively meet the D-2 discharge standard, while that for UV/TiO2 BWTS was 75% rated power. Therefore, the energy cost for UV alone in one test cycle was 0.85P2t (85%P with twice treatment), while that for UV/TiO2 was 0.75Pt (75%P with once treatment). With the above-mentioned results, it can be concluded that for the same treatment processing conditions, UV/TiO2 BWTS can provide

approximately 56% energy savings than UV-alone BWTS in this study. 3.3. Chemical analysis As explained in the introduction, it is suspected that bromide is oxidized by OH during oxidation of seawater, resulting in the formation of HOBr and disinfection by-products (DBPs). In order to address this DBPs formation potential when active substances (e.g., OH, HOBr) are employed for ballast water treatment, the joint Group of Experts on the Scientic Aspects of Marine Environmental Protection-Ballast Water Working Group (GESAMP-BWWG) has suggested a preliminary list of 18 chemicals to be assessed in all BWTS tests [38]. In this study, physicochemical analysis was performed when the maximum UV dose of 260 mJ/cm2 was applied. Salinity, pH, temperature, and dissolved oxygen did not vary before and after treatment (Table 2). ORP showed little enhancement after treatment (Table 2), indicating that residual oxidative species was present during seawater oxidation. Due to ltration, TSS and TOC levels decreased signicantly from 19.4 to 3.8 mg/L and 13.7 to 8.4 mg/L, respectively (Table 2). The concentration of TRO was low (18 lg/L) after UV/TiO2 treatment, which is consistent with the nding that no bromate was detected in any samples after oxidation of seawater (Table 2). The inuent water contained low levels of trichloromethane (TCM), dibromochloromethane (DBCM), monobromoacetic acid (MBAA), tribromoacetic acid (TBAA), monochloroacetic acid (MCAA), dichloroacetic acid (DCAA) (Table 2). 8 compounds including trichloroacetic acid, bromochloroacetic acid, bromodichloroacetic acid, chlorodibromoacetic acid, dibromoacetonitrile, dichloroac etonitrile, bromochloroacetonitrile and trichloroacetonitrile were detected below the detection limits immediately after UV/TiO2 treatment, while tribromomethane (TBM), TCM, DBCM, dichlorobromomethane (DCBM), MBAA, dibromoacetic acid (DBAA), TBAA, MCAA and DCAA were observed in levels of 0.011 lg/L (Table 2). Contrary to expectation, among the detected DBPs, the chlorinated compounds were more predominant than the brominated compounds; TCM (0.846 lg/L) and MCAA (1.04 lg/L) were found at higher concentrations than TBM (0.083 lg/L) and MBAA (0.703 lg/L), respectively. This may due to the fact that the concentration of hypochlorous acid produced from UV/TiO2 treatment of

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Table 2 Physicochemical indicators in inuent water and treated water immediately after UV/TiO2 treatment (T0 h) with the maximum UV dose of 260 mJ/cm2. Mean standard deviation of replicate measurements (i.e., T5, T15 and T25) (n = 3). Test indicators Salinity (PSU) pH Temperature (C) Dissolved oxygen (mg/L) ORP (mV) TSS (mg/L) TOC (mg/L) TRO (lg/L) Bromate (lg/L) Tribromomethane (lg/L) Trichloromethane (lg/L) Dibromochloromethane (lg/L) Dichlorobromomethane (lg/L) Monobromoacetic acid (lg/L) Dibromoacetic acid (lg/L) Tribromoacetic acid (lg/L) Monochloroacetic acid (lg/L) Dichloroacetic acid (lg/L) Trichloroacetic acid (lg/L) Bromochloroacetic acid (lg/L) Bromodichloroacetic acid (lg/L) Chlorodibromoacetic acid (lg/L) Dibromoacetonitrile (lg/L) Dichloroacetonitrile (lg/L) Bromochloroacetonitrile (lg/L) Trichloroacetonitrile (lg/L)
a b c

MDLa n/ab n/ab n/ab n/ab n/ab 0.1 0.2 10 0.11 0.009 0.005 0.009 0.008 0.01 0.01 0.01 0.01 0.013 0.01 0.01 0.008 0.01 0.006 0.002 0.002 0.002

Inuent water (T0 h) 32.5 0.1 8.11 0.01 23.4 0 7.52 0.07 173 3.05 19.4 0.06 13.7 0.1 NDc NDc NDc 0.122 0.04 NDc 0.113 NDc 0.115 0.733 0.153 NDc NDc NDc NDc NDc NDc NDc NDc

Treated water (T0 h) 32.7 0.1 8.12 0.01 23.3 0.1 7.41 0.08 232 2.58 3.8 0.13 8.4 0.2 18 0.4 NDc 0.083 0.846 0.051 0.056 0.703 0.093 0.416 1.04 0.256 NDc NDc NDc NDc NDc NDc NDc NDc

Denotes method detection limit. Denotes not applicable. Denotes not detected.

seawater is higher than that of HOBr, which is different from ozonation and/or chlorination of ballast water treatment [7]. On the other hand, treated ballast water is generally deposited in ballast tanks prior to discharge, and the length of storage time depends on route distance. Several authors have addressed the formation of DBPs in chlorinated and ozonated ballast water [7,39]; however, there is a lack of information about the effects of storage time to DBPs formation in treated ballast water. Fig. 4 shows the time-dependent trends of DBPs formation immediately after treatment, as well as during the 120 h of storage period. Among the measured DBPs, the maximum concentrations of THMs and HAAs were observed immediately after treatment, after which they decreased with storage time extension. The time-effect trends of the observed DBPs were dependent on their formation, stability, as well as TRO level [40]. THMs were relatively volatile, and they were the nal products in the presence of TRO. However, TRO level produced from UV/TiO2 treatment was very low (18 lg/L), it was quickly consumed by organisms present in ballast water rather than reacting with natural organic matter to further produce DBPs. Hence, the concentration of DBPs decreased with increasing storage time. Decline rate of HAAs were signicantly higher than that of THMs, likely due to the fact that typical seawater environment (pH = 8.1) does not contribute to the formation of HAAs [41,42].

1.0

THMs concentrations (g/L)

0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 1.2 1.0 0.9 0.8 0.6 0.4 0.3 0.1 0.0 0 24 48 72 96 120 MBAA DBAA TBAA MCAA DCAA TBM TCM DBCM DCBM

HAAs concentrations (g/L)

4. Conclusions Our trials provide preliminary data illustrating the benets of UV/TiO2 technology to prevent the introduction of MIS via ships ballast water. Compared to UV alone, UV/TiO2 treatment resulted in signicantly lower abundance of individuals in the P50 lm and P10 to <50 lm groups, and reduction of heterotrophic bacteria and E. coli to levels meeting the D-2 discharge standard of the IMO. Although the densities of heterotrophic bacteria and E. coli increased after 120 h of storage period relative to immediately

Storage time (h)

Fig. 4. Concentration of DBPs as a function of storage time of treated samples (i.e., after UV/TiO2 treatment) at salinity: 32.5 PSU, temperature: 23 1 C, pH: 8.15, applied UV dose: 260 mJ/cm2. Error bars represent the standard deviation of replicate measurements (n = 3).

after treatment, the increases following UV/TiO2 treatment were signicantly lower than those following UV alone. Due to the effective biological inactivation of UV/TiO2 BWTS at low UV dose (i.e.,

N. Zhang et al. / Chemical Engineering Journal 243 (2014) 713

13

75%), the operating conditions of the system can be set to administer low UV doses under normal circumstances. Power compensation would serve as an inherent back-up strategy if the BWTS should fail for reasons such as increased ow rate, luminous decay, fouled quartz sleeves or turbid water with lower percentage transmittance. In addition, UV/TiO2 BWTS uses less energy than UV alone because secondary treatment prior to ballast water discharge must be conducted for UV-alone BWTS to meet the D-2 performance standard of the IMO. DBPs formation in the UV/TiO2 BWTS is of much less concern than in systems that employ oxidative methods such as chlorine and ozone [7]. Various ballast water treatment technologies have been developed over the last two decades. Currently, use of strong oxidation (e.g., sodium hypochlorite) has become the predominant technology, followed by UV radiation. Each of these methods have inherent advantages and disadvantages regarding effectiveness, costs, ship and crew safety, power and space requirements, and environmental soundness [43]. Our study clearly demonstrates the potential benets of UV/TiO2 BWTS to reduce invasion risk, and the results presented herein indicate that UV/TiO2 technology is an efcient, environmentally friendly and relatively cost-effective tool for onboard ballast water treatment.

Acknowledgements The authors would like to thank Ahead Ocean Technology Co., Ltd. for the collaboration and this work could not have been carried out without its funding support.

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