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Fluence rate (FR) distribution (optical field) is of great significance in the optimal design of ultraviolet (UV) reactors for disinfection or oxidation processes in water treatment. Since the 1970s, various simulation models have been developed, which can be combined with computational fluidic dynamic software to calculate the fluence delivered in a UV reactor. These models strive for experimental validation and further improvement, which is a major challenge for UV technology in water treatment. Herein, a review of the simulation models of the FR distribution in a UV reactor and the applications of the current main experimental measurement approaches including conventional flat-type UV detector, spherical actinometer, and micro-fluorescent silica detector (MFSD), is presented. Moreover, FR distributions in a UV reactor are compared between various simulation models and MFSD measurements. In addition, the main influential factors on the FR distribution, including inner-wall reflection, refraction and shadowing effects of adjacent lamps, and turbidity effect are discussed, which is helpful for improving the accuracy of the simulation models and avoiding dark regions in the reactor design. This paper provides an overview on the simulation models and measurement approaches for the FR distribution, which is helpful for the model selection in fluence calculations and gives high confidence on the optimal design of UV reactors in regard to present methods., (Copyright © 2021. Published by Elsevier B.V.)

The performance of a medium-pressure (MP) mercury lamp photoreactor is strongly influenced by the spatial photon fluence rate (PFR) distributions which are wavelength-dependent. To address this issue, PFR distributions in an MP lamp photoreactor were measured using a 360-degree response microfluorescent silica detector (MFSD). To accurately express the optical behavior in an MP photoreactor, PFR, MFSD response PFR (PFR MFSD ), and effective germicidal PFR (PFR GER ) were defined and compared. The measured axial and radial PFR MFSD values agreed well with the corresponding results from a simulation model (UVCalc). The PFR and PFR GER were obtained from the measured PFR MFSD by using correction factors calculated by the UVCalc. Under identical UV transmittance (254 nm) conditions (75% and 85%), the weighted average PFR GER values were 13.3-18.7% lower than the corresponding PFR values, indicating that PFR GER , rather than PFR should be used in MP photoreactor design to meet disinfection standards. Based on measured lamp output, medium absorption spectrum, MFSD response, and microbial DNA response spectrum, the detailed relationships between the PFR, PFR MFSD , and PFR GER were elucidated. This work proposes a new method for the accurate description of wavelength-dependent PFR distributions in MP photoreactors, thus providing an important tool for the optimal design of these systems.

After a critical review of the fundamental equations describing photobiological and photochemical processes occurring in a medium exposed to a quasi-collimated monochromatic UV light beam, the analysis in this review is extended to analogous processes driven by polychromatic UV light, such as that emitted by medium pressure mercury-vapor arc lamps. The analysis is based on the Second Law of Photochemistry, namely that all photochemical events must be independent, and the rate of such events must be proportional to the rate of photon absorption. A consistent application of the Second Law of Photochemistry leads to a concept change; hence it is proposed herein to use photon fluence and photon fluence rate, rather than fluence (UV dose) and fluence rate, respectively, in the analysis and interpretation of photobiological and photochemical processes. As a consequence, many equations that have been used in the past must be revised, and some experimental information (e.g. action spectra) needs to be re-analyzed., (© 2015 The American Society of Photobiology.)

Advanced oxidation processes (AOPs) can be used to destroy taste and odour-causing compounds in drinking water. This work investigated both pilot- and full-scale performance of the novel ultraviolet (UV)/chlorine AOP for the destruction of geosmin, 2-methylisoborneol (MIB) and caffeine (as a surrogate) in two different surface waters. The efficiency of the UV/chlorine process at pH 7.5 and 8.5 was comparable to that of the UV/hydrogen peroxide (UV/H2O2) process under parallel conditions, and was superior at pH 6.5. Caffeine was found to be a suitable surrogate for geosmin and MIB, and could be used as a more economical alternative to geosmin or MIB spiking for site-specific full-scale testing., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The ultraviolet (UV) photolysis kinetics of eight sulfonamide (SA) antibiotics was investigated in a quasi-collimated beam apparatus. By using a micro fluorescent silica detector to monitor online the dynamic irradiance fluctuation, the accuracy in fluence quantification could be increased by up to 15%. Solution pH governed the speciation of selected SAs, thus impacting significantly their molar absorption coefficients (ε), fluence-based photolysis rate constants (k'), and quantum yields. An increasing pH induced a hyperchromic effect and a blue shift of the UV-Vis absorption spectra of selected SAs, thus causing the anionic species to show a relatively higher specific ε value than the neutral species at 254 nm. On UV exposure, the photodegradation of selected SAs all followed pseudo-first order reaction kinetics. The SAs with a penta-heterocycle, because of their higher electron densities, exhibited an obviously higher photodegradation rate than those with a hexa-heterocycle. The specific k' values of the neutral and anionic species were in the ranges of (0.30-14.49) × 10(-3) and (0.61-20.90) × 10(-3) cm(2) mJ(-1), respectively. With the specific k' values obtained, it is estimated that only part of SAs can be photodegraded during UV disinfection of water and wastewater, so an advanced oxidation process is necessary if a higher removal of selected SAs is to be achieved., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

UV radiometers are widely employed for irradiance measurements, but their periodical calibrations not only induce an extra cost but also are time-consuming. In this study, the KI/KIO3 actinometer was applied to calibrate UV radiometer detectors at 254 nm with a quasi-collimated beam apparatus equipped with a low-pressure UV lamp, and feasible calibration conditions were identified. Results indicate that a washer constraining the UV light was indispensable, while the size (10 or 50 mL) of a beaker containing the actinometer solution had little influence when a proper washer was used. The absorption or reflection of UV light by the internal beaker wall led to an underestimation or overestimation of the irradiance determined by the KI/KIO3 actinometer, respectively. The proper range of the washer internal diameter could be obtained via mathematical analysis. A radiometer with a longer service time showed a greater calibration factor. To minimize the interference from the inner wall reflection of the collimating tube, calibrations should be conducted at positions far enough away from the tube bottom. This study demonstrates that after the feasible calibration conditions are identified, the KI/KIO3 actinometer can be applied readily to calibrate UV radiometer detectors at 254 nm., (© 2014 The American Society of Photobiology.)

The solar UV/chlorine process has emerged as a novel advanced oxidation process for industrial and municipal wastewaters. Currently, its practical application to oil sands process-affected water (OSPW) remediation has been studied to treat fresh OSPW retained in large tailings ponds, which can cause significant adverse environmental impacts on ground and surface waters in Northern Alberta, Canada. Degradation of naphthenic acids (NAs) and fluorophore organic compounds in OSPW was investigated. In a laboratory-scale UV/chlorine treatment, the NAs degradation was clearly structure-dependent and hydroxyl radical-based. In terms of the NAs degradation rate, the raw OSPW (pH ∼ 8.3) rates were higher than those at an alkaline condition (pH = 10). Under actual sunlight, direct solar photolysis partially degraded fluorophore organic compounds, as indicated by the qualitative synchronous fluorescence spectra (SFS) of the OSPW, but did not impact NAs degradation. The solar/chlorine process effectively removed NAs (75-84% removal) and fluorophore organic compounds in OSPW in the presence of 200 or 300 mg L(-1) OCl(-). The acute toxicity of OSPW toward Vibrio fischeri was reduced after the solar/chlorine treatment. However, the OSPW toxicity toward goldfish primary kidney macrophages after solar/chlorine treatment showed no obvious toxicity reduction versus that of untreated OSPW, which warrants further study for process optimization.

An overlap of the absorption spectrum of the hypochlorite ion (OCl(-)) and the ultraviolet (UV) end of the solar emission spectrum implies that solar photons can probably initiate the UV/chlorine advanced oxidation process (AOP). The application of this solar process to water and wastewater treatment has been investigated in this study. At the bench-scale, the OCl(-) photolysis quantum yield at 303 nm (representative of the lower end of the solar UV region) and at concentrations from 0 to 4.23 mM was 0.87 ± 0.01. Also the hydroxyl radical yield factor (for an OCl(-) concentration of 1.13 mM) was 0.70 ± 0.02. Application of this process, at the bench-scale and under actual sunlight, led to methylene blue (MB) photobleaching and cyclohexanoic acid (CHA) photodegradation. For MB photobleaching, the OCl(-) concentration was the key factor causing an increase in the pseudo first-order rate constants. The MB photobleaching quantum yield was affected by the MB concentration, but not much by the OCl(-) concentration. For CHA photodegradation, an optimal OCl(-) concentration of 1.55 mM was obtained for a 0.23 mM CHA concentration, and a scavenger effect was observed when higher OCl(-) concentrations were applied. Quantum yields of 0.09 ± 0.01 and 0.89 ± 0.06 were found for CHA photodegradation and OCl(-) photolysis, respectively. In addition, based on the Air Mass 1.5 reference solar spectrum and experimental quantum yields, a theoretical calculation method was developed to estimate the initial rate for photoreactions under sunlight. The theoretical initial rates agreed well with the experimental rates for both MB photobleaching and CHA photodegradation., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

The effectiveness of ultraviolet (UV) combined with chlorine as a novel advanced oxidation process (AOP) for drinking water treatment was evaluated in a bench scale study by comparing the rate of trichloroethylene (TCE) decay when using UV/chlorine to the rates of decay by UV alone and UV/hydrogen peroxide (H₂O₂) at various pH values. A medium pressure mercury UV lamp was used. The UV/chlorine process was more efficient than the UV/H₂O₂ process at pH 5, but in the neutral and alkaline pH range, the UV/H₂O₂ process became more efficient. The pH effect was probably controlled by the increasing concentration of OCl⁻ at higher pH values. A mechanistic kinetic model of the UV/chlorine treatment of TCE showed good agreement with the experimental data., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

The fluence rate (FR) distribution in an ultraviolet (UV) reactor was determined experimentally in situ by use of a novel 360° micro fluorescent silica detector (MFSD). The UV response of the MFSD was systematically characterized, and the results indicated that this detector responded only to UV in the range from 210 to 280 nm. The nonlinearity was found to be less than 1% as the FR varied from 0.083 to 2110 μW/cm2. The luminescent signal increased by 0.11% for every degree increase in temperature in the studied range of 0-55 °C. FR distribution tests were performed in different media (air or water) with the water transmittance at either 95% or 85% determined in a 1-cm path length. The FR distribution of the near-lamp region (e.g., radius<50 mm) was well determined with the nearest distance to the sleeve being less than 3 mm. Comparisons were made between the experimental data and the calculations by use of the UVCalc model. This work demonstrates that the MFSD is a novel technique that can provide in situ and real-time measurements of the FR distribution in a UV reactor.

Several organic compounds were used as radical scavengers/reagents to investigate the possibility of the UV/chlorine process being used as an advanced oxidation process (AOP) in the treatment of drinking water and wastewater. The UV/H(2)O(2) process was selected as a reference, so that the results from the UV/chlorine process could be compared with those of the UV/H(2)O(2) process. Methanol was added to active chlorine solutions at both pH 5 and 10 and into hydrogen peroxide samples. The photodegradation quantum yields and the OH radical production yield factors, which are significant in evaluating AOPs, were calculated for both the UV/chlorine and the UV/H(2)O(2) processes. The yield factor for the UV/chlorine process at pH 5 was 0.46 ± 0.09, which is much lower than that of the UV/H(2)O(2) process, which reached 0.85 ± 0.04. In addition to methanol, para-chlorobenzoic acid (pCBA) and cyclohexanoic acid (CHA) were added to active chlorine solutions and to H(2)O(2) solutions, to evaluate the efficiencies of oxidizing these organic compounds. The specific first-order reaction rate constants for the oxidation of pCBA and CHA, using the UV/chlorine process, were lower than those found using the UV/H(2)O(2) process., (© 2010 Elsevier Ltd. All rights reserved.)

In the operation of UV reactors, an important step is to validate if the UV reactor can deliver the design fluence (UV dose) to achieve the required disinfection credit. Free chlorine is used widely in water and wastewater treatment and often is found in the water passing through a UV reactor. Free chlorine is degraded when passing through a UV reactor. This study investigates the potential application of the photodegradation of free chlorine (PFC) to determine the fluence (UV dose) delivered in UV reactors. Using a bench-scale UV reactor, the PFC was investigated at difference UV doses, which also were measured by a biodosimetry method. The results obtained here show that the PFC method has a high correlation with the delivered UV dose (as estimated from the biodosimetry measurements) and is independent of operating conditions, such as flowrate and UV transmittance. In addition, this study indicates that only chloride and chlorate are generated when free chlorine is photodegraded.

The efficacy of UV and vacuum-UV (VUV) disinfection of Bacillus subtilis spores in aqueous suspensions at wavelengths of 172, 222 and 254 nm was evaluated. A Xe(2)* excilamp, a KrCl* excilamp and a low-pressure mercury lamp were used as almost monochromatic light sources at these three wavelengths. The first-order inactivation rate constants at 172, 222 and 254 nm were 0.0023, 0.122 and 0.069 cm(2) mJ(-1), respectively. Therefore, a 2 log reduction of B. subtilis spores was reached with fluences (UV doses) of 870, 21.6 and 40.4 mJ cm(-2) at these individual wavelengths. Consequently, for the inactivation of B. subtilis spores, VUV exposure at 172 nm is much less efficient than exposure at the other two wavelengths, while exposure at 222 nm is more efficient than that at 254 nm, which is probably because triplet energy transfer from DPA to thymine bases at 222 nm is higher than that at 254 nm. This research indicated quantitatively that VUV light is not practicable for microorganism disinfection in water and wastewater treatment. However, in comparison with other advanced oxidation processes (e.g. UV/TiO(2), UV/H(2)O(2) or O(3)/H(2)O(2)) the VUV-initiated photolysis of water is likely more efficient in generating hydroxyl radicals and more effective for the inactivation of microorganisms.

Two Advanced Oxidation Processes, namely vacuum-ultraviolet (VUV) photolysis at 172nm and ultraviolet/hydrogen peroxide (UV/H(2)O(2)) were investigated for the degradation of anatoxin-a in aqueous solutions. Solutions of anatoxin-a-fumarate were treated with VUV light at 172nm with a UV dose of 200 mJ/cm(2), where fumaric acid served as a reference compound for a competition kinetics analysis. The second-order rate constant for the reaction between anatoxin-a and the hydroxyl radical was found to be (5.2+/-0.3)x10(9)M(-1) s(-1) and was independent of pH, temperature, and initial concentration of anatoxin-a. The direct photolysis of anatoxin-a using a medium pressure (MP) UV lamp was also investigated, in which case a UV dose of 1285 mJ/cm(2) was required to degrade anatoxin-a by 88% and 50% at concentrations of 0.6mg/L and 1.8mg/L of toxin, respectively. Treatment of anatoxin-a with a low pressure (LP) UV lamp in the presence of 30mg/L of H(2)O(2) was examined, where it was found that more than 70% of toxin could be degraded at a UV dose of 200 mJ/cm(2). The degradation arises from the oxidation of the toxin by hydroxyl radicals. The addition of H(2)O(2) clearly enhanced the degradation of anatoxin-a, up to a concentration of 40mg/L, after which addition of more H(2)O(2) had little effect on the degradation kinetics of anatoxin-a. The effect of background constituents in the water on the degradation of anatoxin-a was also investigated using natural and synthetically produced model waters.

The action spectra of Bacillus subtilis spores (ATCC6633) and Salmonella typhimurium LT2 were characterized using physical radiometry for irradiance measurements and a multiple target model to interpret the inactivation kinetics. The observed action spectrum of B. subtilis spores deviated significantly from the relative absorbance spectrum of the DNA purified from the spores, but matched quite well with the relative absorbance spectrum of decoated spores. The action spectrum of B. subtilis spores determined in this study was statistically different from those reported in previous studies. On the other hand, the action spectrum of S. typhimurium bacteria matched quite well with the relative absorbance spectrum of DNA extracted from vegetative cells, except in the region below 240nm. It is concluded that the common use of the relative DNA absorbance spectrum as a surrogate for the germicidal action spectrum can result in systematic errors when evaluating the performance of a polychromatic UV light reactors using bioassays. For example, if the weighted germicidal fluence (UV dose) calculated using the relative DNA absorbance spectrum as the germicidal weighting factor is found to be 40mJcm(-2) for a medium pressure lamp UV reactor, that calculated using the relative action spectrum of B. subtilis spores, as determined in this study, would be 66mJcm(-2).

It has been reported that Medium-Pressure (MP) ultraviolet (UV) lamps have an advantage over low-pressure (LP) lamps for water disinfection in terms of the photoreactivation of pure cultured bacteria. However, few studies have investigated the behavior of microorganisms in wastewater. Hence, in this study, the degree of photoreactivation, after UV exposure using both LP and MP lamps, in municipal wastewater samples was examined under a variety of conditions. Pure cultured Escherichia coli was also used to provide a comparison with previous studies. E. coli was found to undergo photoreactivation after both LP and MP exposure. The Colony Forming Ability (CFA) ratios were 0.60 and 0.32, and the percentage of photoreactivation was 50% and 20%, respectively, for LP and MP lamps with a germicidal UV dose of 5 mJ/cm2. However, the advantage of the MP lamp was diminished for larger UV doses, since no photoreactivation was detected when the UV dose was 15 mJ/cm2 for either LP or MP lamps. The microorganisms present in wastewater showed similar results to those of E. coli, however, no significant difference was found between the use of either a LP or a MP lamp. Also, when a UV dose of 40 mJ/cm2 was applied, the percentage photoreactivation was less than 1%, no matter which type of lamp was used. From this work, it is concluded that the selection of the type of UV lamp for wastewater treatment plants, as regards photoreactivation of total coliforms, is not critical as long as the applied germicidal UV dose is greater than 40 mJ/cm2.

The effect of ultraviolet radiation from low- and medium-pressure mercury arc lamps on Cryptosporidium parvum oocysts was studied using a collimated beam apparatus. Experiments were conducted using parasites suspended in both filtered surface water and phosphate buffered laboratory water. Inactivation of oocysts was measured as reduction in infectivity using a CD-1 neonatal mouse model and was found to be a non-linear function of UV dose over the range of germicidal doses tested (0.8-119 mJ/cm2). Oocyst inactivation increased rapidly with UV dose at doses less than 25 mJ/cm2 with two and three log-units inactivation at approximately 10 and 25 mJ/cm2, respectively. The cause of significant leveling-off and tailing in the UV inactivation curve at higher doses was not determined. Maximum measured oocyst inactivation ranged from 3.4 to greater than 4.9 log-units and was dependent on different batches of parasites. Water type and temperature, the concentration of oocysts in the suspension, and the UV irradiance did not have significant impacts on oocyst inactivation. When compared on the basis of germicidal UV dose, the oocysts were equally sensitive to low- and medium-pressure UV radiation. With respect to Cryptosporidium, both low- and medium-pressure ultraviolet radiation are attractive alternatives to conventional chemical disinfection methods in drinking water treatment.