An investigation into reservoir NOM reduction by UV photolysis and advanced oxidation processes

A comparison of four treatment technologies for reduction of natural organic matter (NOM) in a reservoir water was made. The work presented here is a laboratory based evaluation of NOM treatment by UV-C photolysis, UV/H(2)O(2), Fenton's reagent (FR) and photo-Fenton's reagent (PFR). The work investigated ways of reducing the organic load on water treatment works (WTWs) with a view to treating 'in-reservoir' or 'in-pipe' before the water reaches the WTW. The efficiency of each process in terms of NOM removal was determined by measuring UV absorbance at 254 nm (UV(254)) and dissolved organic carbon (DOC). In terms of DOC reduction PFR was the most effective (88% removal after 1 min) however there were interferences when measuring UV(254) which was reduced to a lesser extent (31% after 1 min). In the literature, pH 3 is reported to be the optimal pH for oxidation with FR but here the reduction of UV(254) and DOC was found to be insensitive to pH in the range 3-7. The treatment that was identified as the most effective in terms of NOM reduction and cost effectiveness was PFR.     

Combined UV-C/H2O2-VUV processes for the treatment of an actual slaughterhouse wastewater

In this study, a three-factor, three-level Box-Behnken design with response surface methodology were used to maximize the TOC removal and minimize the H₂O₂ residual in the effluent of the combined UV-C/H₂O₂-VUV system for the treatment of an actual slaughterhouse wastewater (SWW) collected from one of the meat processing plants in Ontario, Canada. The irradiation time and the initial concentrations of total organic carbon (TOC_o) and hydrogen peroxide (H₂O_2o) were the three predictors, as independent variables, studied in the design of experiments. The multiple response approach was used to obtain desirability response surfaces at the optimum factor settings. Subsequently, the optimum conditions to achieve the maximum percentage TOC removal of 46.19% and minimum H₂O₂ residual of 1.05% were TOC_o of 213 mg L^?1, H₂O_2o of 450 mg L^?1, and irradiation time of 9 min. The attained optimal operating conditions were validated with a complementary test. Consequently, the TOC removal of 45.68% and H₂O₂ residual of 1.03% were achieved experimentally, confirming the statistical model reliability. Three individual processes, VUV alone, VUV/H₂O₂, and UV-C/H₂O₂, were also evaluated to compare their performance for the treatment of the actual SWW using the optimum parameters obtained in combined UV-C/H₂O₂-VUV processes. Results confirmed that an adequate combination of the UV-C/H₂O₂-VUV processes is essential for an optimized TOC removal and H₂O₂ residual. Finally, respirometry analyses were also performed to evaluate the biodegradability of the SWW and the BOD removal efficiency of the combined UV-C/H₂O₂-VUV processes.     

Performance of mixed algae for treatment of slaughterhouse wastewater and microbial community analysis

This study investigated organic matter (OM) and nutrient removal efficiency of mixed algal species from slaughterhouse wastewater (SWW) by using photo-bioreactor. For this purpose, different dilution multiples of 10, 4, and 2 were applied to the SWW, and pure wastewater was finally used for algal cultivation. OM and nutrient removal performance in an algal photo-bioreactor were severely affected by the dilution ratio. After 7 days of cultivation, the highest removal percentages of total organic carbon (TOC), total nitrogen (TN), and total phosphorus (TP) were 89.6, 70.2, and 96.2 %, respectively. Furthermore, the changes in eukaryotic algae and cyanobacterial species in the algal photo-bioreactors were investigated using polymerase chain reaction (PCR) and denaturing gradient gel electrophoresis (DGGE) techniques. The results indicated that cyanobacterial species were more efficient than eukaryotic species in removing nutrients from the SWW. This study suggests that mixed algal photo-bioreactors could be used efficiently in the treatment of SWW.

     

Seasonal variability of formaldehyde production from photolysis of rainwater dissolved organic carbon

Photochemical production of formaldehyde (HCHO) was measured in rainwater from 13 precipitation events in Wilmington, North Carolina, USA under conditions of simulated sunlight. HCHO concentrations increased in all samples irradiated with no changes observed in dark controls. HCHO photoproduction rates were strongly correlated with dissolved organic carbon (DOC) suggesting HCHO was derived from direct or indirect photolysis of rainwater DOC. The higher photoproduction rates (0.03–2.9 μM h^?1) relative to those reported for surface waters suggests that rainwater DOC is more photolabile in terms of HCHO production than surface waters. HCHO photoproduction rates were higher in growing season (1.0 ± 1.0 μM h^?1) compared to non-growing season (0.08 ± 0.05 μM h^?1) even when rates were normalized for DOC (6.8 ± 3.6 μM h^?1 mM C^?1 versus 1.8 ± 1.0 μM h^?1 mM C^?1). The higher growing season rate may be related to seasonal differences in the composition of DOC as evidenced by differences in fluorescence per unit carbon of rainwater samples. Irradiation of C18 extracts of rainwater also produced HCHO, but at lower rates compared to corresponding whole rain samples, suggesting that hydrophyllic components of rainwater play a role in HCHO photoproduction. Our results indicate that photolysis of rainwater DOC produces significant amounts of HCHO, and possibly other low molecular weight organic compounds, likely increasing its reactivity and bioavailability.     

The degradation of dissolved organic nitrogen associated with melanoidin using a UV/H2O2 AOP

The aim of this study was to examine the simultaneous degradation of dissolved organic nitrogen (DON) and associated colour from wastewater containing melanoidins by an advanced oxidation process (AOP). UV irradiation of H2O2 was used as the mechanism to create the hydroxyl radical for oxidation. Melanoidins are large nitrogenous organic compounds that are refractory during biological wastewater treatment processes. The simultaneous degradation of DON and colour, present as a result of these compounds, was investigated using an AOP. The oxidation process was much more capable of removing colour (99% degradation), dissolved organic carbon (DOC) (50% degradation) and DON (25% degradation) at the optimal applied dose of hydrogen peroxide for the system (3300 mg l(-1)). This indicated that colour and DON removal were decoupled problems for the purpose of treating melanoidin by an AOP and thus colour removal can not be used as an indication of DON removal Colour was caused by organic molecules with molecular weight greater than 10 kDa. Oxidation caused a partial reduction of the DON (41-15% of the total dissolved nitrogen) and DOC (29-14% of the DOC) associated with the large molecular weight fraction (>10 kDa) and almost complete colour removal (87-3% of the total colour). The degraded DON was mostly accounted for by the formation of ammonia (31% of the nitrogen removed from the large fraction) and small molecular weight compounds (66% of the nitrogen removed from the large fraction). The degraded DOC appeared to be mostly mineralised (to CO2) with only 20% of the degraded compounds appearing as small molecular weight DOC.     

Improvement of DOC removal by multi-stage AOP-biological treatment

The single and multi-stages advanced oxidation process (AOP)-biological treatments were evaluated to apply for drinking water treatment, especially for the water containing less susceptible dissolved organic carbon (DOC) to ozone, comparing with the ozonation-biological treatment. Minaga reservoir water and the secondary effluent from a Municipal wastewater treatment plant were used as dissolved organic matter (DOM) solutions. DOC removals after 60 min AOP-biological treatment were 62% and 41% in the Minaga reservoir water and the secondary effluent, respectively, whereas those in the ozonation-biological treatment only 40% and 15% of DOC were removed, respectively. The result indicated that the single-stage AOP-biological treatment could improve DOC removal in comparison with the single-stage ozonation-biological treatment. This is because the AOP mineralized both biodegradable dissolved organic carbon (BDOC) produced in the early stage of oxidation and non-biodegradable dissolved organic carbon (NBDOC), whereas only BDOC was mineralized by further ozonation and NBDOC was not oxidized in the ozonation-biological treatment. The multi-stage treatment could not improve DOC removal in comparison with the single-stage treatment in the ozonation-biological treatment for the secondary effluent containing less susceptible DOC to ozone. However, the multi-stage AOP-biological treatment significantly reduced DOC and achieved 71% of DOC removal by 4 times repetition of 15 min oxidation, whereas DOC removal was 41% in the single-stage AOP-biological treatment for the same oxidation time. The improvement of DOC removal by the multi-stage AOP-biological treatment was due to BDOC removal as a radical scavenger by subsequent biological treatment in the early stage of oxidation and direct mineralization in the latter stage of oxidation.     

Mechanisms of photosynthetic inactivation on growth suppression of Microcystis aeruginosa under UV-C stress

This study aims to investigate the effects of UV-C irradiation on photosynthetic processes of Microcystis aeruginosa to unravel the mechanism(s) involved in how and in what ways UV-C mediates growth suppression and cellular recovery. Changes in the concentration of photosynthetic pigments, photochemical efficiency, PS II core protein (D1) content, and the coding genes expressions were measured. The results indicate that UV-C doses at 20–200 mJ cm⁻² lead to rapid reduction in gene expression of both psbA (for D1) and cpc (for phycocyanin), but the suppression was short term and recoverable within 3 d of post-UV incubation. Conversely, UV-C doses at ?50 mJ cm⁻² could induce marked decline in photochemical efficiency (represented by the optimal PS II quantum yield, F_V/F_M, and the effective PS II quantum yield, Y) as well as decreases in D1 content and water soluble pigments (phycoerythrins, phycocyanins, allophycocyanins) in M. aeruginosa during the post UV-C incubation period. The results suggest that interruption of both the light energy harvesting apparatus (especially the water soluble pigments) and the photochemical process mainly accounted for the growth suppression effect in UV-C irradiated M. aeruginosa.     

Synergistic adsorption and advanced oxidation activated by persulfate for degradation of tetracycline hydrochloride using iron-modified spent bleaching earth carbon

At present, tetracycline hydrochloride (TCH) is a widely used antibiotic, and is often detected in water, posing a serious harm to human and ecological health. In this study, spent bleaching earth (SBE) was pyrolyzed to obtain spent bleaching earth carbon (SBE@C) and the nano Fe⁰/SBE@C prepared after zero-valent iron loading was adopted to remove TCH in water for the first time. The combination of nano Fe⁰/SBE@C and PS, the strong adsorption of SBE@C coupled with the oxidation of free radicals could achieve TCH efficient removal. The effects of nano Fe⁰ load, nano Fe⁰/SBE@C dosage, solution initial pH, and PS/TCH molar ratio on TCH removal efficiency in nano Fe⁰/SBE@C?+?PS system were studied. The results indicate that the optimal reaction conditions are 5% nano Fe⁰ load, 0.2 g/L nano Fe⁰/SBE@C dosage, initial pH of 3, PS/TCH molar ratio of 100:1. Under these conditions, TCH removal efficiency could reach 91%. Meanwhile, response surface methodology (RSM) was applied to predict optimal value of reaction conditions. The removal efficiency corresponding to the predicted optimal conditions was consistent with the actual removal efficiency obtained from the experiment. Moreover, six reaction systems were tested, and TCH removal efficiency in the SBE@C?+?PS system was 22.6%. When nano Fe⁰ was loaded on SBE@C, TCH removal efficiency in Fe⁰/SBE@C?+?PS system increased to 78.2%, in which TCH was first adsorbed on the surface of nano Fe⁰/SBE@C, and then was degraded by the oxidation of SO₄^?? and ?OH. Totally, the nano Fe⁰/SBE@C?+?PS system displayed excellent TCH removal efficiency, good stability and reusability, exhibiting a promise toward TCH removal.

     

Effect of inorganic and organic solutes on zero-valent aluminum-activated hydrogen peroxide and persulfate oxidation of bisphenol A

The effect of varying inorganic (chloride, nitrate, sulfate, and phosphate) and organic (represented by humic acid) solutes on the removal of aqueous micropollutant bisphenol A (BPA; 8.8 μM; 2 mg/L) with the oxidizing agents hydrogen peroxide (HP; 0.25 mM) and persulfate (PS; 0.25 mM) activated using zero-valent aluminum (ZVA) nanoparticles (1 g/L) was investigated at a pH of 3. In the absence of the solutes, the PS/ZVA treatment system was superior to the HP/ZVA system in terms of BPA removal rates and kinetics. Further, the HP/ZVA process was not affected by nitrate (50 mg/L) addition, whereas chloride (250 mg/L) exhibited no effect on the PS/ZVA process. The negative effect of inorganic anions on BPA removal generally speaking increased with increasing charge in the following order: NO₃^? (no inhibition)?<?Cl^? (250 mg/L)?=?SO₄^2??<?PO₄^3? for HP/ZVA and Cl^? (250 mg/L; no inhibition)?<?NO₃^??<?SO₄^2??<?PO₄^3? for PS/ZVA. Upon addition of 20 mg/L humic acid representing natural organic matter, BPA removals decreased from 72 and 100% in the absence of solutes to 24 and 57% for HP/ZVA and PS/ZVA treatments, respectively. The solute mixture containing all inorganic and organic solutes together partly suppressed the inhibitory effects of phosphate and humic acid on BPA removals decreasing to 46 and 43% after HP/ZVA and PS/ZVA treatments, respectively. Dissolved organic carbon removals were obtained in the range of 30 and 47% (the HP/ZVA process), as well as 47 and 57% (the PS/ZVA process) for the experiments in the presence of 20 mg/L humic acid and solute mixture, respectively. The relative Vibrio fischeri photoluminescence inhibition decreased particularly for the PS/ZVA treatment system, which exhibited a higher treatment performance than the HP/ZVA treatment system.     

Study on dissolved organic carbon in precipitation in Northern China

Dissolved organic carbon (DOC) was measured in 483 precipitation samples collected at 10 sites in Northern China from December 2007 to November 2008. The annual volume-weighted mean (VWM) concentrations and wet deposition fluxes of DOC for 10 sites ranged from 2.4 to 3.9 mg C/L and 1.4 to 2.7 g C m^?2 yr^?1, respectively. The proportion of DOC to total organic carbon (TOC) was 79% on average, suggesting that a significant fraction of TOC was present as insoluble particulate organic carbon. Due to intensive domestic coal use for house heating and smaller dilution of scavenged organic carbon, higher VWM concentrations of DOC were observed during winter and spring than during summer and autumn. When precipitation events were classified via air mass back-trajectories, the mixed trajectories from SE and NW always corresponded to significantly higher DOC than those from SE or NW alone, coinciding with the centre of a low pressure system moved eastward and the wind direction changed from southeast to northwest. The results also showed that each site had a similar seasonal variation for DOC wet deposition flux. The largest flux occurred during the rainy season, and the lowest flux appeared during winter months. The product of the TC/DOC ratio and the DOC flux yielded an average TC wet deposition flux of 3.2 g C m^?2 yr^?1 in Northern China, accounting for 8.6% and 22% of the carbon sink magnitude (37 g C m^?2 yr^?1) in terrestrial ecosystems and anthropogenic carbon emissions (14 g C m^?2 yr^?1), respectively. This indicates that atmospheric wet deposition of TC is a significant carbon flux that cannot be neglected in regional models of the carbon cycle, and should be considered along with dry deposition in the removal mechanism for carbon from regional atmosphere.     

Fenton-like degradation of nalidixic acid with Fe3+/H2O2

The Fenton-like degradation of nalidixic acid was studied in this work. The effects of Fe³⁺ concentration and initial H₂O₂ concentration were investigated. Increasing the initial H₂O₂ concentration enhances the degradation and mineralization efficiency for nalidixic acid, while Fe³⁺ shows an optimal concentration of 0.25 mM. A complete removal of nalidixic acid and a TOC removal of 28 % were achieved in 60 min under a reaction condition of [Fe³⁺]?=?0.25 mM, [H₂O₂]?=?10 mM, T?=?35 °C, and pH?=?3. LC–MS analysis technique was used to analyze the possible degradation intermediates. The degradation pathways of nalidixic acid were proposed according to the identified intermediates and the electron density distribution of nalidixic acid. The Fenton-like degradation reaction of nalidixic acid mainly begins with the electrophilic attack of hydroxyl radical towards the C₃ position which results in the ring-opening reaction; meanwhile, hydroxyl radical attacking to the branched alkyl groups of nalidixic acid leads to the oxidation at the branched alkyl groups.     

Photocatalytic oxidation of pesticide rinsate

Pesticide rinsate has been considered as one of the major threats for the environment. In this study, photocatalysts such as TiO2 and O3 were used to promote the efficiency of direct UV photolysis to prevent such wastewater pollution. Carbofuran (a carbamate pesticide) and mevinphos (an organophosphate pesticide) with a concentration of 100 mg/L were selected as the test pesticide rinsates. Parent pesticide compound, COD, and microtoxicity analysis were employed to investigate the effect of photocatalyst on the degradation efficiency of pesticide in rinsate. It was found that the photocatalytic oxidation process (UV/O3, UV/TiO2) showed much higher COD removal and microtoxicity reduction efficiency for pesticide rinsate than did direct UV photolysis under the imposed conditions, suggesting that photocatalytic oxidation processes such as UV/O3 and UV/TiO2 could be a better alternative to treat pesticide rinsate. In addition, it was noted that increasing the initial pH of mevinphos rinsate to a basic level was required to reach higher COD removal efficiency and positive microtoxicity reduction efficiency while it was not necessary for the treatment of carbofuran rinsate.     

Decolorizing of lignin wastewater using the photochemical UV/TiO2 process

Studies on applying the photochemical UV/TiO2 oxidation process to treat the lignin-containing wastewater for dissolved organic carbon (DOC), color and reducing A254 (the absorption at the wavelength of 254 nm) have been carried out. The data obtained in this study demonstrate that the UV/TiO2 process is effective in oxidizing the lignin thus reducing the color and DOC of the wastewater treated. The combined UV/TiO2 treatment can achieve better removal of DOC and color than the UV treatment alone. Color removal, based on American Dye Manufacture Index (ADMI) measurement, is greater than 99% if the pH is maintained at 3.0 with the addition of 1 g l(-1) TiO2. When 10 g l(-1) TiO2 is applied, the oxidation reduction potential (ORP) value is reached to result in an 88% removal of both DOC and color. A model was developed based on the variation of ORP during the photochemical reaction to simulate the decoloring process. The proposed model can be used to predict the color removal efficiency of the UV/TiO2 process.     

紫外活化过硫酸盐工艺降解水中磺胺二甲氧嘧啶动力学特征与机理

采用紫外活化过硫酸盐(UV/PS)工艺降解典型磺胺类抗生素磺胺二甲氧嘧啶(SDM),比较单一紫外(UV)、单一过硫酸盐(PS)和UV/PS对SDM的去除效果,考察各因素对降解动力学的影响,并探究其降解机理,对SDM及其中间产物进行毒性测定和风险评价.结果显示,UV/PS可以加速SDM降解,反应速率常数分别是单一UV和单...     

Photocatalytic degradation of lignin using Pt/TiO2 as the catalyst

Photocatalytic degradation of lignin was studied with the use of catalysts TiO(2) and Pt/TiO(2). The influence of several experimental parameters, i.e. pH, catalyst dosage and illumination on lignin degradation was investigated. The results showed that application of UV irradiation alone has almost no effect on the reduction of dissolved organic carbon (DOC) and American Dye Manufacture Institute value (ADMI). However, the addition of TiO(2) and Pt/TiO(2) reduced the original DOC (251 mg l(-1)) by more than 40% within 30 min of treatment and the reaction can be simulated with pseudo-first order kinetics. Rapid degradation of lignin was observed in acidic solution using either TiO(2) or Pt/TiO(2) as the catalyst compared to high pH cases. The content of Pt in the Pt/TiO(2) catalyst is 1%. In addition, too much catalyst addition has not increased the DOC and ADMI reduction proportionally. The investigation also indicated that the photocatalytic degradation rates could be enhanced 1-6 times faster after doping TiO(2) with Pt in different pH cases. A modified Nernst type model was adopted to simulate the decoloring process using TiO(2) and Pt/TiO(2) based on the profiles of oxidation reduction potential during the photocatalytic reaction. The developed equation can be used to predict the color removal efficiency of lignin wastewater by the photocatalytic process.     

Remediation of DDTs contaminated soil in a novel Fenton-like system with zero-valent iron

Application of a novel Fenton-like system with zero-valent iron, EDTA and Air (ZVI/EDTA/Air) was investigated to degrade dichlorodiphenyltrichloroethane (DDT), dichlorodiphenyldichloroethane, and dichlorodiphenyldichloroethylene (DDE) in the actual contaminated soil from an organochlorine pesticide site. It was found DDTs in the soil were effectively degraded by the system at room temperature, ambient atmosphere pressure and near neutral pH. The dosages of EDTA and ZVI were the dominant factors influencing the removal of contaminants. An increase of EDTA from 0.05 to 0.2 mM and ZVI from 1 to 5 g L^?1 improved the removal of the contaminants significantly. However, excessive amount of EDTA led to a negative effect on the degradation process. Meanwhile, EDTA was simultaneously degraded so as to avoid the secondary pollution risk on soil remediation. Only a small amount of 4,4′-DDE and 2,2-bis(4-chlorophenyl)-1-chloroethylene (4,4′-DDMU) generated as the intermediates of DDT degradation during the process. Our investigation suggests that the Fenton-like system is a promising alternative for remediation of organochlorine pesticides contaminated soils.     

Evaluation of ion exchange resins for the removal of dissolved organic matter from biologically treated paper mill effluent

In this study, the efficiency of six ion exchange resins to reduce the dissolved organic matter (DOM) from a biologically treated newsprint mill effluent was evaluated and the dominant removal mechanism of residual organics was established using advanced organic characterisations techniques. Among the resins screened, TAN1 possessed favourable Freundlich parameters, high resin capacity and solute affinity, closely followed by Marathon MSA and Marathon WBA. The removal efficiency of colour and lignin residuals was generally good for the anion exchange resins, greater than 50% and 75% respectively. In terms of the DOM fractions removal measured through liquid chromatography–organic carbon and nitrogen detector (LC–OCND), the resins mainly targeted the removal of humic and fulvic acids of molecular weight ranging between 500 and 1000 g mol^?1, the portion expected to contribute the most to the aromaticity of the effluent. For the anion exchange resins, physical adsorption operated along with ion exchange mechanism assisting to remove neutral and transphilic acid fractions of DOM. The column studies confirmed TAN1 being the best of those screened, exhibited the longest mass transfer zone and maximum treatable volume of effluent. The treatable effluent volume with 50% reduction in dissolved organic carbon (DOC) was 4.8 L for TAN1 followed by Marathon MSA – 3.6 L, Marathon 11 – 2.0 L, 21K-XLT – 1.5 L and Marathon WBA – 1.2 L. The cation exchange resin G26 was not effective in DOM removal as the maximum DOC removal obtained was only 27%. The resin capacity could not be completely restored for any of the resins; however, a maximum restoration up to 74% and 93% was achieved for TAN1 and Marathon WBA resins. While this feasibility study indicates the potential option of using ion exchange resins for the reclamation of paper mill effluent, the need for improving the regeneration protocols to restore the resin efficiency is also identified. Similarly, care should be taken while employing LC–OCND for characterising resin-treated effluents, as the resin degradation is expected to contribute some organic carbon moieties misleading the actual performance of resin.     

Recent progress on application of UV excilamps for degradation of organic pollutants and microbial inactivation

Excilamps as modern mercury-free sources of narrow-band UV radiation represent an attractive alternative in environmental applications. This review focuses on recent studies on the water and surface decontamination with excilamps by means of direct photolysis and advanced oxidation processes. To date, direct photolysis and advanced oxidation processes (AOPs) such as UV/H₂O₂, UV/Fenton and UV/O₃ have been applied for degradation of organic compounds (mainly, phenols, dyes and herbicides) in model aqueous solutions. Special emphasis is placed on studies combining UV irradiation (as a pre-treatment or post-treatment step) with biological treatment. In this review, the efficiencies of direct UV, UV/H₂O₂ and UV/TiO₂ processes for inactivation of a variety of pathogenic microorganisms in water and on surfaces are discussed. The analysis of the literature shows that more works need to be done on scaling up the processes, degradation/mineralization of target pollutant(s) in real effluents and evaluation of energy requirements.