Journal of Photochemistry and Photobiology B: Biology 93 (2008) 155161

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Journal of Photochemistry and Photobiology B: Biology

journal homepage: www.elsevier.com/locate/jphotobiol

Effectiveness of solar disinfection using batch reactors with non-imaging aluminium reectors under real conditions: Natural well-water and solar light
C. Navntoft a,d, E. Ubomba-Jaswa b, K.G. McGuigan b, P. Fernndez-Ibez c,*
a

Comisin Nacional de Energa Atmica CNEA, Av. Gral. Paz 1499, cp BNK1650 San Martn, Buenos Aires, Argentina Department of Physiology and Medical Physics, Royal College of Surgeons in Ireland, Dublin 2, Ireland c Plataforma Solar de Almera CIEMAT, P.O. Box 22, 04200 Tabernas, Almera, Spain d Escuela de Posgrado, Universidad Nacional de San Martn, Peatonal Belgrano 3563, B1650ANQ San Martn, Argentina
b

a r t i c l e

i n f o

a b s t r a c t
Inactivation kinetics are reported for suspensions of Escherichia coli in well-water using compound parabolic collector (CPC) mirrors to enhance the efciency of solar disinfection (SODIS) for batch reactors under real, solar radiation (cloudy and cloudless) conditions. On clear days, the system with CPC reectors achieved complete inactivation (more than 5-log unit reduction in bacterial population to below the detection limit of 4 CFU/mL) one hour sooner than the system tted with no CPC. On cloudy days, only systems tted with CPCs achieved complete inactivation. Degradation of the mirrors under eld conditions was also evaluated. The reectivity of CPC systems that had been in use outdoors for at least 3 years deteriorated in a non-homogeneous fashion. Reectivity values for these older systems were found to vary between 27% and 72% compared to uniform values of 87% for new CPC systems. The use of CPC has been proven to be a good technological enhancement to inactivate bacteria under real conditions in clear and cloudy days. A comparison between enhancing optics and thermal effect is also discussed. 2008 Elsevier B.V. All rights reserved.

Article history: Received 18 February 2008 Received in revised form 1 July 2008 Accepted 25 August 2008 Available online 6 September 2008 Keywords: Compound parabolic collector Solar disinfection Escherichia coli Natural well-water

1. Introduction Many communities in developing countries cannot afford a conventional means of water treatment. As a result a large number of the population who live in these areas do not have access to safe water. This can lead to widespread occurrence of waterborne diseases most frequently in the form of diarrhoea. Infectious diarrhoea is also the leading cause of illness and death in children less than 5 years of age. An economical and simple way to inactivate waterborne pathogens is required. Water disinfection using the solar disinfection (SODIS) process relies on the synergistic effect of sunlight and temperature upon bacteria [13]. A great part of the research in understanding the mechanism of this process has been done using transparent plastic bottles exposed to sunlight under different operating conditions. Results have shown that 6 h of solar exposure is sufcient to inactivate most bacterial pathogens in contaminated water when using bottles of up to 2 L in volume [4,5]. The modern resurgence in SODIS was started by Acra et al. [6] who reported that enteric bacteria were inactivated after exposure to 6 h of sunlight. Subsequently other organisms have been tested,

* Corresponding author. Fax: +34 950 365015. E-mail addresses: navntoft@cnea.gov.ar (C. Navntoft), eubombajaswa@rcsi.ie (E. Ubomba-Jaswa), kmcguigan@rcsi.ie (K.G. McGuigan), pilar.fernandez@psa.es (P. Fernndez-Ibez). 1011-1344/$ - see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.jphotobiol.2008.08.002

including: Salmonella typhimuirum, Shigella dysenteriae, Escherichia coli, Vibrio cholera and Pseudomonas aeuriginosa [1,4,7,8], protozoan oocysts of Cryptosporidium parvum and cysts of Giardia muris [9], the yeast Candida albicans; the fungus, Fusarium solani [10] and Polio virus [11]. A controlled eld trial conducted immediately after a cholera epidemic also revealed that SODIS participants were seven times less likely to contract cholera [12]. The suitability of the SODIS technique for countries with a high incidence of waterborne disease is further illustrated by the fact that these countries lie in the latitude lines of 30N and 30S and hence receive sufcient sunlight to apply SODIS. When exposed to sunlight, standard SODIS reactor bottles are only illuminated on the upper side so that a large fraction of the available radiation can not reach the water. In order to increase the radiation reaching the bottles, there have been several attempts to concentrate solar radiation using reecting surfaces. Kehoe et al. [4] found that the decay constants increased two fold by the use of aluminium foil attached to the back of the bottles. Rijal et al. [13] used wall reectors and observed improved efciencies which they attributed solely to the increase in water temperature of the system. Martin Dominguez et al. [14] found that reective solar boxes could reduce the disinfection time to 34 h. Even though all the mentioned works achieved some degree of enhancement by the use of the reectors, none of them analyzed which is the best concentrating optics to enhance the radiation reaching the bottles in SODIS.

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Depending on their shape and geometry, concentrating systems or mirrors can be classied into imaging systems and non-imaging systems. Image forming systems focus an image of the sun at a point, which is where the absorber is positioned. A typical example is a parabolic mirror. They only work with rays parallel to the axis of the parabola which means that they can only use direct solar radiation and on clear days only. On the other hand, non-imaging systems have a diffuse focus, and no image is formed. The concentrated rays are homogeneously distributed in the absorber. Their main advantage is that they concentrate diffuse radiation. Hence, they do not rely solely on direct solar radiation and are effective even on cloudy days. In addition, they concentrate radiation independently of the direction of sunlight and do not require sun tracking in contrast to direction dependant image forming systems. The SODIS process relies heavily on the UV-A wavelengths present in sunlight (315400 nm). Solar UV-A as received at sea level, is composed of roughly similar portions of both direct and diffuse electromagnetic radiation. On sunny days, the solar UV-A spectrum is composed of $60% direct and $40% diffuse solar radiation [15]. Given the diffuse nature of the UV-A and the cylindrical shape of the bottles, the use of concentrating systems based on non-imaging optics with low concentrating factor has obvious potential compared to imaging optics-based systems. Compound parabolic concentrators (CPCs) are concentrators utilising non-imaging optics. Other reecting systems tested in previous studies [13,14,16] have a varying concentration during the day because they are essentially image forming systems and depend on the angle of incidence of the sun on the reector. A major advantage of CPC systems is that the concentration factor remains constant for all values of sun zenith angle within the acceptance angle limit. When non-imaging optics is used to design a mirror for a cylindrical absorber, the result obtained is a compound parabolic concentrator (CPC). CPC mirrors have been widely used and tested in the eld of photocatalysis to enhance the UV radiation reaching the photocatalyst and it has been proven that the CPC is the best optic to use to concentrate the solar UV spectrum [17]. Based on these arguments, the assessment of the use of CPC mirrors to enhance SODIS is needed. This work reports results on the evaluation of the use of CPC mirrors to enhance SODIS efciency under real solar radiation conditions in cloudy and clear days. For this proposal, suspensions of E. coli in real well-water were used for disinfection studies. 2. Materials and methods 2.1. PET bottles and glass tubes The shape and dimensions of plastic bottles used for SODIS experiments are not standardized. From the practical point of view all bottles perform with similar efciency even though the amount of radiation reaching the water is not necessary the same. The surface of the bottles is usually irregular and the shape is, in some parts of the bottle, not cylindrical but rather hexagonal. A correct assessment of the radiation entering the system would require detailed optical analysis and calculations for each particular bottle. In order to avoid this obstacle, bottles were replaced with borosilicate glass tubes which were closed at both ends. One end was completely closed and the other had a sampling valve tted, as can be seen in Fig. 1a. Each tube had dimensions of 1.50 m length, 0.05 m outer diameter, 1.8 mm wall thickness and 2.5 L internal volume. Transparent PET bottles are opaque below wavelengths of 320 nm and transmittance might be as high as 8590% in UV-A (320400 nm) wavelengths [7]. Borosilicate glass tubes have a transmittance of 45% in the UV-B (280320 nm) and of 8990% in the UV-A range [18]. In order to assess any efciency difference

Length = 1.50 m Diameter = 0.05m Closed end Sampling valve Optic axis

C = 90

CPC mirror

Fig. 1. (a) Glass tube conguration. (b) Design of CPC for the glass tube experiments. (c) Experimental tube tted in CPC mirror inclined 37 with respect to horizontal facing south.

arising from the transmittance, a comparison experiment was performed. The plastic bottle used for this experiment was a 2 L-bottle with hexagonal cross sectional shape, 9 cm equivalent diameter and 30 cm height. Both the bottle and the tube were exposed to sunlight under the same atmospheric, radiometric and meteorological conditions in duplicated experiments. 2.2. CPC mirrors We dene: aperture area = A; absorber area = Aabs; Sun zenith angle on the concentrator = h; acceptance angle of the CPC = hc; concentration factor = C = A/Aabs. The fundamental problem of radiation concentration is how can radiation which is incident on A and uniformly distributed over a range of angles (h 6 hc) be concentrated onto the smaller absorber area Aabs without the need for repositioning the system as the value of h varies [19]. For a cylindrically shaped SODIS reactor the concentrating system is twodimensional. In this case, the second law of thermodynamics states

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that the maximum possible concentration or ideal concentration is Cideal = 1/sin hc. In the case of SODIS and given the diffuse nature of the UV-A spectrum [16], only a homogeneous distribution of light on the absorber tube is required, not a high concentration. Hence, a system with a concentration factor of 1 (C = 1) sun was designed. Then, hc = 90 and the shape of the mirror is dened by an involute to the absorber as can be seen in Fig. 1b. The aperture of the system is 15.7 cm and is numerically equal to the perimeter of the absorber. Due to the nonimaging nature of the reectors, the entire absorber is homogeneously illuminated at all times, even on cloudy days. The CPC mirrors were built with highly reective aluminium sheets type 320 G ALANOD anodized aluminium of 0.5 mm thickness (Alanod Aluminium GmbH, Ennepetal, Germany). The manufacturer reports a reectivity of 82% for the UV and 85% for the rest of the solar spectrum. The reectivity of the mirrors was assessed with a reectometer from Devices and Services (USA), model ISR, measurement spectra of 635685 nm centred at 660 nm and a precision in measurement of 0.2%. In order to assess the inuence of the material degradation upon the SODIS process, the tubes were tested with old and new CPC mirrors of the same material. The older CPCs had been exposed to eld conditions for 3 years with relatively low maintenance. 2.3. Solar experiments All experiments were performed under natural solar radiation at the Plataforma Solar de Almera (P.S.A.), Spain, located at 37840 N and 2340 W. All the experiments were conducted in duplicate on twin systems (tube + CPC) under the same meteorological conditions to ensure reproducibility of results, and each sample was plated in triplicate. Tests started at 10:30 am and nished at 15:30 pm local time. Samples were taken after 15, 30, 60, 90, 120, 150, 180, 240 and 300 min of solar exposure. All the evaluated systems were inclined at 37 and facing South as shown in Fig. 1c. The inclination corresponds to the latitude of the Plataforma Solar de Almera. This inclination value maximizes the annual energy collection, enhancing the radiation reaching the system during the winter months with a slight reduction during the summer [20]. Solar UV irradiance was measured with a global UV radiometer (295385 nm, Model CUV3, Kipp and Zonen, Netherlands) inclined at 37, the same inclination as the systems. 2.4. Bacteria

Re-growth counts of bacteria were determined for all experiments, by leaving the last two samples at room temperature for 24 and 48 h. After 24 and 48 h the plate count method as described above was used to determine bacterial counts on both LB agar plates and Endo agar (SigmaAldrich, USA) plates. Endo agar is a selective media, specic for the detection of coliforms and enteric organisms in sources such as drinking water. Endo agar was also used as a way to suppress and prevent growth of any non-coliforms or non-enteric organisms that might have grown during the 24 and 48 h period and might interfere with accurate counts of E. coli K-12. All samples of the experiments reaching the detection limit were evaluated in this way at the end of the experiment and bacterial re-growth after stopping illumination was not observed within 24 and 48 h. 2.5. Water Natural well-water was used in all experiments. The water was extracted from a well located in the PSA area with a depth of approx. 200 m. The content of natural microorganisms is of around 100200 CFU/ml. The procedure to determine the background contamination was the same as that described in previous section. The concentration of naturally occurring organisms was determined by the plate enumeration technique using LB agar and was found to be 100-200 CFU/ml. These organisms were identied as non-coliforms and non-enteric in nature due to their presentation as either irregular, colourless colonies on Endo agar or the complete lack of growth also on Endo agar. These studies were carried out using natural well-water so that the microbiological and chemical environment within which the SODIS inactivation occurred was as realistic as possible. Consequently, distilled water and other highly contaminated wastewaters (like municipal WW) were discarded as models of this study. For similar reasons, the well-water was not autoclaved before each experiment in order to preserve the chemical integrity of the original water matrix. A single batch of 100 L of well-water was withdrawn at once so that the same stock of water was used for all the experiments, so that possible variations in the natural wellwater composition did not occur. Consequently all experimental results could be compared. Table 1 shows general physical water parameters averaged during the period of the experimental series. 3. Results 3.1. CPC inuence on clear sunny days

E. coli was used as a model target microorganism since it is widely used as an indicator of faecal contamination in water. E. coli K-12, ATCC 23631 was propagated in Luria Broth nutrient medium (Millers LB Broth, Sigma-Aldrich, USA) and incubated at 37 C with constant agitation on a rotary shaker at 100 rpm for 24 h. The stationary phase of bacterial growth yielded a concentration of 109 CFU/mL. For all experiments, the range of initial concentrations (C0) of E. coli was from 106107 CFU/mL. Previous studies by the authors (unpublished) have shown that this 1-log-unit variation in starting population had no inuence on the observed inactivation kinetics. E. coli suspensions were centrifuged at 800g for 10 min and re-suspended in PBS and inoculated in the 2.5-L tube to reach the required cell density. Samples were serially diluted in PBS and plated. Every sample was diluted at 1/10 relationship up to three dilutions (D0, D1, D2, and D3) and consequently plated on Luria agar (SigmaAldrich, USA). The detection limit for this method of quantication is 4 CFU/mL. Inoculated samples were incubated at 37 C for 24 h before counting. As a control, half of the volume of the rst sample (7 mL) was kept in the dark at 37 C during the whole experiment and re-plated at the same time as the last sample of the experiment.

Fig. 2a shows the results of the comparison between the bottle and the tube with and without CPC to assess any difference in SODIS efciency due to material transmittance and also to the CPC. Another tube was kept in the dark under the same eld conditions as a control to guarantee the viability of the cells in the tube in the absence of solar radiation. Experiments were performed on clear sunny days.

Table 1 Average physical and chemical properties of the well-water used in the experiments Natural well-water at PSA Cl NO 3 SO 4 F Br PO3 4 pH Turbidity 355 mg/L 22 mg/L 329 mg/L 1 mg/L 2 mg/L 0.5 mg/L 7.3 12 NTU Na+ NH4+ K+ Mg2+ Ca2+ HCO 3 Conductivity Bacteria 370 mg/L 6 mg/L 11 mg/L 64 mg/L 122 mg/L 500 mg/L 2300 lS/cm 100 CFU/mL

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10 10 10 10 10 10 10 10

Controls Dark

60 50 40

3.2. CPC inuence on cloudy days Fig. 2b shows the results of similar experiments performed on cloudy days. In this case the bottle was not tested since it was previously shown to have a lower efciency even in full sunshine. In this case only the system with the CPC reectors reached the detection limit. In these systems several factors contribute to the results shown in Fig. 2a and b. When turbidity of the water is very low (15 NTU), the SODIS process is dominated by the amount of sunlight reaching the absorber [4]. On clear days, the direct component of sunlight predominates. Approximate contributions of direct and diffuse sunlight for the UV-A spectrum are of 60% and 40%, respectively [15]. This means that the energy needed for SODIS to reach detection limit will eventually be reached in both systems. Nevertheless, the reectors contribute by delivering more energy in less time, producing a faster inactivation rate and reaching the detection limit one hour before. As stated earlier, the system without the CPC is only exposed to the sun on the front side whereas that with the CPC has the entire tube illuminated. On cloudy days, most of the available UV-A is in the diffuse form with a negligible value for the direct component. In this case, the reectors distribute all of the diffuse radiation reaching the aperture onto the absorber. The system without reectors receives mainly the circumsolar diffuse radiation that comes directly from the direction of the sun and not from the entire sky hemisphere. This is known as forward scattered radiation and is very low on cloudy days. This explains the fact that the system tted with the CPC reaches detection limit and while the system with no CPC does not. In terms of optical path length, only the forward scattered radiation reaches the system without reectors and it must pass through 5 cm of water optical path length while the system with CPC receives radiation from the entire sky hemisphere and must only go through 2.5 cm because the whole tube is illuminated. 3.3. Mirror degradation The reectivity measurements performed on new mirrors reported homogeneous values over all the mirror of 82%. Those performed on 3 year old mirrors reported non-homogeneous values between (27.0 0.5)% and (72.0 0.5)% of surface reectivity over the length of the material. The use of old and new CPC mirrors for solar disinfection was evaluated on both clear and cloudy days. No improvement was seen on clear days in the system that had the old CPC compared to the tube system without reectors (data not shown). As stated previously, on clear days the inuence of the CPC only allows a faster inactivation, so the degradation of the mirror retards this effect and inactivation times are the same in the case of none and old CPC. On cloudy days, the advantage of even an old degraded CPC can still be observed (Fig. 2b). Both CPC (old and new) systems reached the detection limit in cloudy days. The system without CPC did not. The performance curves of the tube in (Fig. 2a) and the old CPC (Fig. 2b) are similar. It is interesting to note that the old CPC is capable of collecting so much diffuse radiation on cloudy days that it matches the inactivation efciency observed for tube-only systems on sunny days. The water temperature of the systems was monitored for each sample in all the experiments. The temperature proles were similar to those recorded for 2 L PET bottles. None of the tests reached a temperature higher than 33 C. In the dark the temperature of the water increased by around 6 C while in sunlight all the systems increased from 2021 C to 3033 C. This small increase of temperature during the 5 h-exposure can not explain the bacterial inactivation observed but can affect the inactivation kinetics during the process. Berney et al. [1] reported sensitivity to mild heat

Bacteria Conc. (CFU/ml)

UV Irradiance

30 20

Tube+CPC

Tube

Bottle DL
10 0

11:00

12:00

13:00

14:00

15:00

Local time (hh:mm)

10 10 10 10 10 10 10 10
7

Controls

60 50

Bacteria Conc. (CFU/ml)

No CPC

UV Irradiance
40

30
3

20

Old CPC
1

New CPC
11:00 12:00 13:00 14:00

DL
15:00

10 0

Local time (hh:mm)

Fig. 2. E. coli K12 inactivation during real sunlight exposure on clear days (a) with real sunlight exposure in a glass tube with CPC (-.-), without CPC (-d-), PET bottle (-N-) dark control (-j-); and on cloudy days (b) in a glass tube with new CPC (-.-), old CPC (-N-), without CPC (-d-). Solid line () is the solar UV (295385 nm) irradiance. Dashed line () shows the detection limit (DL). Each point represents the average measurements and error bars show standard deviation from triplicate measurements taken in duplicated experiments.

The plots show from 10:30 to 15:30 (x-axis) because the experiments were conducted during that period although points are only plotted up until the time when the bacterial concentration decreased below the detection limit (DL). Tube inactivation reaches the detection limit one hour before the bottle. This can be attributed to the fact that the borosilicate glass tube has a 45% UV-B transmittance (compared to 0% for PET) and a 5% advantage over PET in the UV-A. Variations in UVA transmittance of both materials for the specic widths used in the experiments yielded an average difference of just 5.3% (data not shown). Larger differences in transmittance can be seen beyond UVA but since very little UVB and no UVC are present in terrestrial natural sunlight the effect of the different diameter of the glass tube and the bottle [7] can be considered negligible. Both glass tubes, with and without CPC, reached the detection limit (4 CFU/mL). It can be seen that the system with the CPC reached the detection limit one hour before the system with no CPC. In terms of UVA-ux, the system with CPC reached detection limit after receiving 150 kJ/m2 (Table 2) from the sun calculated as the integral of the solar UVA irradiance (W m2) on the time of exposure until DL was reached (s) , while that with no CPC needed 210 kJ/m2. This represents 40% more energy required to achieve the same result on clear days with the non-CPC system. Hence the system with CPC is more efcient in terms of energy usage.

UV Irradiance (W/m2)

UV Irradiance (W/m2)

C. Navntoft et al. / Journal of Photochemistry and Photobiology B: Biology 93 (2008) 155161 Table 2 Main characteristics of the tests presented in the experimental section Date
a

159

Solar system 2007 2007 2007 2007 2007 2007 2007 Glass tube Bottle/No CPC Tube/No CPC Tube/(new) CPC Tube/No CPC Tube/old CPC Tube/new CPC

Solar conditions Dark Sunny Sunny Sunny Cloudy Cloudy Cloudy

Averageb solar UVA irradiance (W m2) 35 5 35 5 35 5 28 8 28 8 28 8

Ci

(CFU mL1)

Cf

(CFU mL1)

Exposure to reach DL (h)/UVA-uxe (kJ/m2) 3/340 60 2/210 30 1.5/150 20 2/200 50 1.5/140 40

Minimummaximum temperature (C) 21.327.5 21.329.5 21.530.4 21.033.0 20.728.7 20.331.2 20.233.0

Figure

29 29 29 29 24 24 24
a b

May May May May May May May

(6.1 0.6) 106 (5.3 0.4) 106 (4.3 0.4) 106 (5.23 0.14) 106 (4.8 0.5) 106 (5.5 0.3) 106 (3.5 1.1) 106

(7.0 3.0) 105 DL DL DL (3.8 1.1) 103 DL DL

Fig. Fig. Fig. Fig. Fig. Fig. Fig.

2a 2 2a 2a 2b 2b 2b

All the experiments were performed in duplicate in twin systems under the same climate conditions from 10:30 to 15:30 local time. The average for the 5 h duration of the experiment. c Ci: initial bacterial concentration (CFU mL1) d Cf: nal bacterial concentration (CFU mL1). DL: when zero CFU was detected, concentration was the detection limit (DL: 4 CFU/mL). Each value of bacterial concentration is the average measurement and errors are standard deviation from triplicate measurements taken in duplicated experiments. e Accumulated UVA-ux calculated as the integral of the solar UVA irradiance (W m2) on the time of exposure until DL was reached.

Log10 N(CFU ml )

above a temperature of 45 C for E. coli, S. typhimurium and S. exneri, while V. cholerae was already susceptible above 40 C. The temperatures experienced in this work are relatively lower compared to those values. 3.4. Modeling with Gearaerd and Van Impe inactivation model tting tool The Gearaerd and Van Impe inactivation model tting tool (GInaFIT) was used for analysing different congurations of the solar systems under sunny and cloudy conditions. The following models were used: log-linear regression, log-linear + tail, log-linear + shoulder, log-linear + shoulder + tail, Weibull model, biphasic model, biphasic + shoulder [21]. All models were run for each inactivation curve and the values of the root mean sum of squared errors (RMSE) were compared. The RMSE is considered to be the most simple and informative measure of goodness-of-t for linear and nonlinear models [21]. The model with the smallest RMSE was considered the best t for the respective inactivation curve. If two models had the same or similar RMSE values the simplest model was considered to t best. TDL and FDL values (exposure time and solar UVA-ux required to reduce plate counts to the detection limit DL) were calculated using the best-t model of GInaFIT (Table 3). These ts show that
Table 3 Fitting results of the experimental data using the Gearaerd and Van Impe inactivation model tting tool (GinaFiT) Solar system Fitting model Parameters Shoulder length; kmax (min1) Sunny conditions Bottle Geeraerd shoulder Glass tube Geeraerd shoulder Glass Geeraerd shoulder tube + new CPC Cloudy conditions Glass tube Geeraerd shoulder and tail Glass tube + old Geeraerd shoulder CPC Glass Geeraerd shoulder tube + new CPC 48 6; 0.11 0.01 26 3; 0.15 0.01 16 8; 0.20 0.02 TDL (min) FDL (kJ/m2)

7 6 5 4 3 2 1 0 0 60

Sunny conditions Geeraerd shoulder model

-1

Bottle

Tube Tube+CPC
120 180
DL

Log10 N(CFU ml )

7 6 5 4 3 2 1 0 0 60 120

-1

Cloudy conditions Geeraerd shoulder model Geeraerd shoulder + tail model

No CPC

Tube+new CPC

Tube+old CPC
DL

180

240

300

Time (min)
Fig. 3. Inactivation curves of E. coli K12 during real sunlight exposure on clear days (top) in a glass tube with CPC (-.-), without CPC (-d-), PET bottle (-N-), and on cloudy days (bottom) in a glass tube with new CPC (-.-), old CPC (-N-), without CPC (-d-). Lines represent theoretical ts using the Gearaerd and Van Impe inactivation model tting tool (GinaFiT) [21].

the experiments carried out in the glass tube using the new CPC yields the fastest inactivation rate (kmax) compared with the other systems evaluated. All kinetics results obey the Geeraerd shoulder model as expected for the SODIS process [1], except for the case of the tube without CPC mirror under cloudy conditions which obeys to the Geeraerd shoulder and tail model (Fig. 3). 4. Discussion In previous SODIS experiments it was established that the minimum temperature at which a synergy effect can be observed is around 4550 C for E. coli K12 [7]. Since in our experiments the temperature never exceeded 33 C, synergy and thermal effects were ignored so that the bacterial inactivation observed can only be attributed to the effect of solar radiation. There are a number of pioneering studies that have tried to enhance disinfection using some kind of solar thermal system. Martin Dominguez et al. painted sections of the bottles with black paint so that the water could reach a higher temperature [14]. Rijal et al. circulated water over a black surface in an enclosed casing which was transparent to UV-A light [13]. Saitoh et al. made a system that enhanced temperature by using a solar collector attached to a double glass envelope container [22]. All of these studies have

174.6 0.8 330 60 120.0 0.3 210 30 87.3 0.3 140 20

41 3; 0.14 0.01 log(Nres) = 3.60 0.03 26 5; 0.15 0.01 120.0 0.5 200 50 18 9; 0.16 0.04 88.0 0.4 130 30

TDL and FDL values (time and ux received required to reach DL) from real sunlight exposure of the different solar systems studied.

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achieved different degrees of success with respect to enhancing the heat transfer to the contaminated water. From the solar thermal point of view, bottles or tubes painted partially or totally with conventional black paint are among the least efcient systems for converting sunlight into heat [23]. The most economic solar collectors have an average conversion efciency of around 30% [24]. Painted bottles or tubes have a somewhat lower efciency than these. According to the principles of heat transfer [23,25], it takes approximately 12 h to heat 1 L of water inside a painted bottle from 20 to 45 C, assuming summer weather conditions, global irradiances of around 800 W/m2 and a 30% conversion efciency. In winter, depending on ambient temperature, the system would not reach the desired temperature mainly due to heat losses to the environment. Previous works have tried to couple a solar thermal collector to a radiation collector device [22] to address this problem. More efcient solar thermal collectors are available but their cost is prohibitively high to be considered as a part of a SODIS system. From the optical point of view and with the use of a CPC, the solar UV-A radiation reaching the system is limited by the transmittance of the tube or bottle and the reectivity of the mirror. The transmittance of most PET bottles and borosilicate glass tube is around 8590%. The reectivity of the mirror can vary according to the material used to build the reectors. In most cases it is above 80% [26]. The major advantage of UV-A light is that it still reaches the Earths surface on cloudy days, so solar radiation eventually gets into the water and reaches the bacteria. However, it should be noted that solar collector systems do not reach the desired temperature in cloudy days. Clearly it is much more protable to invest efforts to enhance the optics of radiation collection in SODIS systems than to enhance the thermal component. In view of these results, the use of CPC enhances SODIS inactivation on both clear and cloudy days. On clear days the CPC effect is a faster inactivation of the bacteria. On cloudy days, only systems with CPC reectors were inactivated to below the detection limit. This highlights a major advantage of CPC-enhanced SODIS since it overcomes the problems associated with process interruption due to cloudiness. It is important to mention that until now most of research on SODIS has shown that complete inactivation is not reached on cloudy days [5]. Although the systems have not been tested with completely overcast skies, the statement remains the same, all radiation reaching the aperture will reach the absorber. In contrast, the system with no reectors will receive very little radiation. The water used in the experiments was transparent with turbidity of less than 5 NTU. In eld conditions, water turbidity can go up to 200 NTU. Under such conditions an important attenuation of sunlight is expected as mentioned by Kehoe et al. [4]. In these cases, the difference in inactivation efciency between systems with and without CPC reectors is expected to be larger on both clear and cloudy days. The path length of light inside the water when the CPC are used reduces to half of that with no reectors. Given that the attenuation of sunlight is exponential according to the BeerLambert law, an important enhancement of the process in turbid water systems with CPC is expected. The attenuation of light in turbid water was investigated by Sommer et al. [27]; this issue will be addressed with further experiments under real conditions as a complementary study of this work. It is widely accepted that UVA radiation (315400 nm) mediates its biological effects on bacteria mainly via reactive oxygen species (ROS), such as superoxide radicals, hydroxyl radicals, hydrogen peroxide, and singlet oxygen [28]. In natural waters and wastewaters subjected to oxidation processes, oxidation of contaminants initiated by CO is always in competition with oxi3 dation by hydroxyl radical and, depending on the type of process,

with oxidation by other oxidizing species, or phototransformation by UV light [29]. Formation rates of CO cannot exceed those of 3 hydroxyl radicals, while the main scavengers of both radicals are dissolved natural organic matter and, if present, hydrogen peroxide. The high content of carbonates CO /bicarbonates HCO 3 3 present in the well-water used in this work may be a limiting factor for the SODIS process. HCO reacts with the hydroxyl radicals, 3 producing the less reactive anion radical CO (Eqs. (1) and (2)). 3 This radical shows a wide range of reactivity with organic molecules but it is mainly a selective electrophilic reagent, and its reactions are slower than those of OH. In addition, HCO induces photo 3 absorption which protects bacteria from light. This screening effect limits the light penetration into the bacterial suspension [30].

OH HCO ! CO H2 O 3 3 OH CO2 ! CO OH 3 3

1 2

Given that SODIS is usually used under rough eld conditions degradation of reectivity is likely to be a problem for whichever reective material is used. The older CPCs were exposed to only moderate eld conditions and yet suffered an important decrease in the reectivity after 3 years of exposure. Therefore, material degradation should not be overlooked for any reector used together with SODIS systems. The cost of the aluminium mirror itself is similar to that of the bottle or even higher depending on the quality, so the use of reectors is justied in larger SODIS systems that provide drinking water for several households. Nevertheless alternative materials that are less reective and consequently cheaper could be used. Another benet of the use of CPCs is that they enhance solar disinfection without using any additives in the water. Previous works have shown that solar disinfection can be improved by adding a photocatalyst in suspension to the system [31]. Even though this makes the process more effective, it poses another problem because the catalyst has to be removed from the water matrix. Since this work clearly shows the benet of using CPC mirrors to enhance SODIS inactivation on both sunny and cloudy days it is reasonable to expect CPC-enhanced SODIS systems to inactivate more resistant water pathogens like bacterial spores and protozoa, whose resistance to traditional SODIS is much greater than that of bacterial cells. Further research work will be addressed to explore the capabilities of CPC-enhanced SODIS on disinfection of water containing such pathogens.

5. Conclusions

 The use of CPCs to enhance SODIS has been tested with natural well-water and natural sunlight conditions. On clear days, a faster inactivation rate is obtained in the system with CPC compared to that without reectors. On cloudy days inactivation to below the detection limit is only achieved using systems tted with CPCs. This technological enhancement can be used to design future larger scale systems to treat high volumes of water for several households.  The degradation of the mirrors under eld conditions should not be underestimated and has to be considered if systems are exposed outdoors for extended periods of time. After 3 years of exposure, non-homogeneous degradation of mirrors was observed through the reectivity measurements. New CPC reectivity was around 82% while values between 27% and 72%were recorded for older CPCs. The faster inactivation rate on clear sunny days was not signicant for systems with old CPCs compared to systems with no reectors. However, on cloudy days both new and older CPCs produced inactivations

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to below the detection limit, a feat which is un-matched by systems without CPCs. This means that even with degradation, a CPC provides a major advantage.  The CPC has been proven as a SODIS enhancement technology, allowing more radiation to reach the absorbing volume leading to a reduction in the SODIS exposure time and allowing the treatment of higher volumes of water on the same day.

6. Abbreviations CPC: compound parabolic collector; SODIS: solar disinfection. Acknowledgements The authors thank to Miss Aranxta Fernandez for making reectivity measurements of mirrors and for her helpful suggestions. This work was nanced by the SODISWATER project (EU Contract: INCO-CT-2006-031650) and Doctoral Fellowship from ANPCyT and Grant MAE-AECI 2006-2007 (Spain) for C. Nanvtoft. References
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