Photoactivation and photoregeneration of TiO2/PAC mixture applied in suspension in water treatments: approach to a real application.

The process TiO2/PAC/UV-vis has been under study and compared with the isolated treatments of adsorption and photocatalysis determining possible synergies between adsorption and photocatalysis of target antibiotics: amoxicillin, enrofloxacin, sulfadiazine, and trimethoprim. The characterization of the TiO2/PAC mixture was carried out via FESEM and FTIR. Moreover, a kinetic study has been performed. The effect of UV-vis radiation and the type of matrix was analyzed in TiO2/PAC/UV-vis process. The performance of this treatment has been monitored during three cycles, evaluating also the regeneration of TiO2/PAC mixture by UV-vis light. TiO2/PAC/UV-vis process allowed the removal of the antibiotics in the range 90-100% (an average removal of 93% of the initial concentration) after 60 min of treatment. However, only amoxicillin showed a significant synergy applying TiO2/PAC/UV-vis process. Regarding matrix effect, no influence of the matrix type (ultrapure water or treated wastewater) was observed. Since PAC tends to be deactivated gradually, the TiO2/PAC/UV-vis process performance decreases after each cycle in a 15% average. Finally, regeneration via UV-vis light started to be effective after a total of 4 h of regeneration.

Comparative adsorption of ciprofloxacin on sugarcane bagasse from Ecuador and on commercial powdered activated carbon.

This work examined the adsorption capacity of sugarcane bagasse (SB) for the removal of ciprofloxacin (CPX) from water using batch experiments and a fixed bed column and compared its adsorption performance with a powdered activated commercial carbon (PAC). Both adsorbents achieved a similar percentage removal of about 78% with doses of 3 g L-1 of SB and 0.3 g L-1 of PAC (20 mg L-1 initial CPX concentration at 30 °C). The maximum removal was obtained at a pH between 6 and 8. SB adsorption isotherms were fitted to the Langmuir, BET and Freundlich models showing a maximum adsorption capacity of 13.6 mg g-1. The kinetic data for both SB and PAC fitted the pseudo second-order model (R2 = 0.99). The adsorption process was faster on the SB (65% of elimination in the first 5 min) than on the PAC. The study of the adsorbent properties shows that SB is a macroporous solid with a specific surface area 250 times smaller than PAC. The thermodynamic results show that SB adsorption was physical and exothermic. The main suggested interactions between CPX and SB are electrostatic attraction, hydrogen bonding and dipole-dipole interactions. The experiments carried out in a fixed bed show that the adsorption capacity at breakthrough increases with the bed height. The adsorption capacity at saturation time was 9.47 mg g-1 at a flow rate of 3 mL min-1, a bed height of 14 cm, and a diameter of 1.5 cm. The experimental data were fitted to the Bohart-Adams model (R2 = 0.98). These results highlight the capacity of sugarcane bagasse to adsorb ciprofloxacin from water, illustrating its potential as a low-cost adsorbent.

Antibiotics removal from aquatic environments: adsorption of enrofloxacin, trimethoprim, sulfadiazine, and amoxicillin on vegetal powdered activated carbon.

This study addresses the growing concern about the high levels of antibiotics in water, outlining an alternative for their removal. The adsorption of four representative antibiotics from commonly used families (fluoroquinolones, ß-lactams, trimethoprim, and sulfonamides) was performed over vegetal powdered activated carbon. The evolution of the adsorption was studied during 60 min for different initial antibiotic concentrations, not only individually but also simultaneously to determine competitive adsorption. Moreover, this research studied the adsorption isotherms and kinetics of the process, as well as the pH influence; FTIR of the activated carbon before and after adsorption was carried out. Trimethoprim and sulfadiazine showed more affinity for the adsorbent than amoxicillin and enrofloxacin. This trend might be attributed to their structure, capable of stablishing stronger π-π interactions with the adsorbent, which showed high affinity for the active sites of the adsorbent via FTIR. In addition, the sorption isotherms of trimethoprim followed a Langmuir type isotherm, amoxicillin followed a Freundlich type isotherm, and enrofloxacin and sulfadiazine followed both. The antibiotics followed pseudo-second-order kinetics. Sulfadiazine and amoxicillin gave better performances in acidic conditions. By contrast, the sorption of trimethoprim was favored in basic environments. Variations of pH had a negligible effect on the removal of enrofloxacin.

Study of Evolution of Microbiological Properties in Sewage Sludge-Amended Soils: A Pilot Experience.

Large amounts of sewage sludge are generated in urban wastewater treatment plants and used as fertilizer in agriculture due to its characteristics. They can contain contaminants such as heavy metals and pathogenic microorganisms. The objective of this research work is to study, in real conditions, the evolution of microbial concentration in agricultural soils fertilized by biologically treated sewage sludge. The sludge (6.25 tons Ha-1) was applied in two agricultural soils with different textures and crops. A microbiological (total coliforms, Escherichia coli, Staphylococcus aureus, Enterococcus sp., Pseudomonas sp., Salmonella sp. and total mesophylls) and physical-chemical characterization of the sludge, soils and irrigation water were carried out. The evolution of these parameters during sowing, growth and harvesting of crops was studied. Initially, sewage sludge had a higher concentration of microorganisms than soils. Irrigation water also contained microorganisms, fewer than sewage sludge amendment but not negligible. After amendment, there were no differences in the microbiological evolution in the two types of soil. In general, bacterial concentrations after crop harvest were lower than bacterial concentrations detected before sewage sludge amendment. Consequently, the application of sludge from water treatment processes did not worsen the microbiological quality of agricultural soil in this study at real conditions.

Identification of free-living amoebas and amoeba-resistant bacteria accumulated in Dreissena polymorpha.

To identify the free-living amoeba (FLA) and amoeba-resistant bacteria (ARB) accumulated in zebra mussels and in the water in which they are found, mussels were collected at two locations in the Ebro river basin (North East Spain). FLAs and bacteria were isolated from mussel extracts and from natural water. PCR techniques were used to identify the FLAs and endosymbiont bacteria (Legionella, Mycobacterium, Pseudomonas and cyanobacteria), and to detect Giardia and Cryptosporidium. The most frequently found FLAs were Naegleria spp. The presence of Legionella, Mycobacterium and Pseudomonas inside the FLA was demonstrated, and in some cases both Legionella and Pseudomonas were found together. Differences between FLAs and ARB identified inside the mussels and in the water were detected. In addition, Escherichia coli, Clostridium perfringens, Salmonella spp. and Enterococcus spp. were accumulated in mussels in concentrations unconnected with those found in water. The results show the ability of the zebra mussel to act as a reservoir of potentially pathogenic FLAs, which are associated with potentially pathogenic ARB, although the lack of association between microorganisms inside the mussels and in the water suggests that they are not useful for monitoring microbiological contamination at a specific time.

Visible light plays a significant role during bacterial inactivation by the photo-fenton process, even at sub-critical light intensities.

The aim of this research is to clarify the contribution of sunlight wavelengths, irradiance and Fe2+/H2O2 during bacterial disinfection by the photo-Fenton process in clear surface waters. We considered different solar spectrum distributions (visible, UVA-Visible), sub-critical irradiances (0-400 W/m2), focusing on the action modes of E. coli inactivation by the constituents involved in the composite process, at low µM reactants concentration (Fe2+/H2O2) in in ultrapure (MQ) water. We report that solar disinfection improved with Fenton reagents (photo-Fenton process) is a reality from very low light irradiance values (200 W/m2), and made possible even without the presence of UVA radiation, even when using low quantities of the Fenton reagents (0.5 mg/L Fe2+, 5 mg/L H2O2). Under light exposure, H2O2 was found to augment the intracellular Fenton process and Fe2+ to initiate further, distinct oxidative actions. Finally, validation was performed in Lake Geneva water over a wider irradiance range, where the photo-Fenton process was found to be reagent-dependent in low irradiance, shifting to light-driven in the higher values.

Performance comparison of commercial TiO2: separation and reuse for bacterial photo-inactivation and emerging pollutants photo-degradation.

This research aims to compare the disinfection and degradation effectiveness in water of a commercial suspension of nano-TiO2 (TiO2Levenger) with the standard TiO2Degussa P25. Photo-inactivation and photo-degradation experiments were conducted with UVA-vis light. Concerning the disinfection, the effects of TiO2 dose (0-2 g/l), water matrix, bacterium type (Gram-positive or Gram-negative), and bacterial regrowth after the photo-treatments were studied for each catalyst. The experimental results show that Enterococcus sp. (Gram-positive) was more resistant to the photo-treatments than Escherichia coli (Gram-negative) for both catalyst; however, postirradiation trends showed similar behavior for both bacteria, favoring regrowth for short-treated cells and decay for longer-treated ones. Caffeine was selected as a model substance of pharmaceuticals and personal care products. In terms of caffeine removal, the effects of TiO2 dose (0-2 g/l) and water matrix were analyzed. Besides, the comparison between mechanical coagulation-flocculation-decantation and simple decantation of TiO2 was carried out. The results show that simple decantation allowed the recovery of 97.5% of TiO2 Degussa P25 and TiO2 Levenger within 1 day of simple decantation, while applying the proposed mechanical coagulation-flocculation decantation 99.7% of recovery of both catalysts was achieved in 2 hours. Finally, the subsequent reuse of both catalysts was proved with little loss of efficiency in terms of photo-disinfection during the four cycles. Nevertheless, the standard TiO2 Degussa P25 photo-degradation efficiency of caffeine decreases considerably as compared to commercial suspension of TiO2 Levenger concerning the reutilization.

Electrochemical advanced oxidation processes for Staphylococcus aureus disinfection in municipal WWTP effluents.

This paper presents the Staphylococcus aureus inactivation in a simulated wastewater treatment plant effluent by different electrochemical techniques, including the photo-electro-Fenton process. S. aureus, dissolved organic carbon (DOC), total oxidants and H2O2 concentrations, as well as pH, were monitored during the assays. An electrolytic cell, including a UVA lamp, a gas diffusion electrode (GDE) as cathode and an IrO2 anode, was used to conduct the experiments under galvanostatic conditions (20 mA). Low inactivation (-0.4) and low DOC removal were achieved within 120 min when applying the GDE-IrO2 system, in which bacteria disinfection was caused by the generated H2O2. When light was combined with GDE-IrO2, the process efficiency noticeably increased (-3.7 log inactivation) due to the synergistic effect between UVA and H2O2. Introducing iron (5 mg L-1 Fe2+) into the system also produced higher disinfection and DOC mineralization. The electro-Fenton process (GDE-IrO2+Fe2+) led to a bacterial reduction of -0.9 log units and DOC reduction of 14%, while with the photo-electro-Fenton process (GDE-IrO2+UVA + Fe2+) -5.2 units of bacteria and 26% of DOC were removed. Increasing the current intensity (20 mA, 30 mA and 40 mA) in the photo-electro-Fenton system increased H2O2 production and, consequently, augmented the bacterial inactivation (-5.2 log, -6.2 log and -6.5 log, respectively). However, mineralization extent slightly increased or remained practically the same. When comparing the influence of Fe2+ and Fe3+ on photo-electro-Fenton, similar S. aureus inactivation was observed, while DOC removal was higher with Fe2+ (31%) than with Fe3+ (19%). Finally, by testing the system with a Ti anode, the direct anodic oxidation contribution of the IrO2 anode was identified as negligible.

Synergistic effect of the presence of suspended and dissolved matter on the removal of cyanide from coking wastewater by TiO2 photocatalysis.

This study assesses the influence of the presence of suspended and dissolved matter on the efficiency of TiO2 photocatalysis for the removal of cyanide from coking wastewater. Photocatalytic processes were carried out at basic pH (pH 9) with titanium dioxide (1 g/L), artificial radiation (290-800 nm) and during different time periods (20-100 min). The first assays applied in aqueous solutions achieved promising results in terms of removing cyanide. The maximum cyanide removal obtained in coking wastewater was 89% after 80 min of irradiation in the presence of suspended and dissolved matter. The presence of suspended matter composed of coal improves the efficiency of the photocatalytic process due to the synergistic effect between carbon and TiO2. The absence of dissolved matter also improves the process due to the minimization of the hydroxyl radical scavenging effect produced by carbonate and bicarbonate ions. On the other hand, the presence of certain species in the real matrix such as silicon increases the activity of the titanium dioxide catalyst. In consequence, the improvement achieved by the photocatalytic process for the removal of cyanide in the absence of dissolved matter is counteracted.

Combined photo-fenton-SBR processes for the treatment of wastewater from the citrus processing industry.

In this study, the photo-Fenton process was combined with a sequencing batch reactor (SBR) for the treatment of synthetic samples of citrus wastewater (CWW). An experimental design based on the surface response methodology was applied to assess the individual and combined effects of several operating parameters (CODinitial, Fe3(+) concentration and H2O2 concentration) on the photo-Fenton treatment efficiency (DOC removal) with the aim of optimizing the process. The experimental results obtained under optimal conditions for CWW with high CODinitial (10000 mgO2/L) showed a partial degradation of organic matter of around of 61% (measured as DOC). Thereafter, the photo-Fenton effluent was neutralized and clarified before being subjected to the SBR reactor. The results show degradation yields up to 93% of the initial DOC removal without producing undesired side effects, using a hydraulic retention time (HRT) of 1.59 d. The final effluent contained a concentration of organic matter (measured as COD) of 120 mg O2/L.

Sediment quality evolution (2001-2011) in the Ebro River basin (Spain).

Spatio-temporal variations in sediment quality (20 sample sites) of the Ebro River basin between 2001 and 2011 have been assessed. The self-organizing map classified the sediment samples according to similarities in their chemical compositions. Its powerful visualization tools helped establish the main pollution contribution on each sample. Most of the samples showed low values of the mean-probable effect concentration quotient through time. However, six samples presented several quality issues related to some trace elements or polycyclic aromatic hydrocarbons. Finally, geoaccumulation index values calculated using estimates of background trace element concentrations suggested anthropogenic influences in more than half of the samples.

Potential risk assessment of trace elements and PAHs in sediment samples of the Ebro River basin (Spain).

This study was carried out in order to assess potential toxicity of hazardous pollutants (8 trace elements and 8 polycyclic aromatic hydrocarbons) in 20 sediment samples of the Ebro River basin (Spain) sampled in 2009. Mean-probable effect concentration quotient (m-PECQ) was found to range from 0.03 to 0.79. Two sites were classified as high priority sites in order to take future remediation actions due to their high m-PECQ value (>0.5). Worst-case scenario in equilibrium partitioning approach showed that acid volatile sulfide (AVS) content was greater than total trace element concentration in all samples. However, 4 sediments were classified as degraded due to the high AVS content measured (>50 mmol/kg). Principal component analysis classified the samples according to similar chemical characteristics and revealed that industrial activities are the main source of pollution of the basin.

Potential toxicity of polycyclic aromatic hydrocarbons and organochlorine pesticides in sediments from the Ebro River basin in Spain.

This study was carried out to estimate the potential toxicity of 8 Polycyclic Aromatic Hydrocarbons (PAHs) and 5 organochlorine pesticides (OCPs) in sediments in the Ebro River Basin (20 sampling points) according to different methodologies. Detection limit (DL) concentrations were used for compounds reported below the DL (worst-case scenario). The majority of PAH concentrations were found to be below their method detection limit. DL concentrations for OCPs were above the threshold values set by one guideline. In such cases, no toxicity assessment was carried out. It should be noted that no sediment is expected to cause adverse effects on the benthic species living in these sediments according to the methodologies applied.

Experimental design approach applied to the elimination of crystal violet in water by electrocoagulation with Fe or Al electrodes.

An experimental design methodology was applied to evaluate the decolourization of crystal violet (CV) dye by electrocoagulation using iron or aluminium electrodes. The effects and interactions of four parameters, initial pH (3-9), current density (6-28 A m(-2)), substrate concentration (50-200 mg L(-1)) and supporting electrolyte concentration (284-1420 mg L(-1) of Na(2)SO(4)), were optimized and evaluated. Although the results using iron anodes were better than for aluminium, the effects and interactions of the studied parameters were quite similar. With a confidence level of 95%, initial pH and supporting electrolyte concentration showed limited effects on the removal rate of CV, whereas current density, pollutant concentration and the interaction of both were significant. Reduced models taking into account significant variables and interactions between variables have shown good correlations with the experimental results. Under optimal conditions, almost complete removal of CV and chemical oxygen demand were obtained after electrocoagulation for 5 and 30 min, using iron and aluminium electrodes, respectively. These results indicate that electrocoagulation with iron anodes is a rapid, economical and effective alternative to the complete removal of CV in waters. Evolutions of pH and residual iron or aluminium concentrations in solution are also discussed.

Solar photochemical treatment of winery wastewater in a CPC reactor.

Degradation of simulated winery wastewater was studied in a pilot-scale compound parabolic collector (CPC) solar reactor. Total organic carbon (TOC) reduction by heterogeneous photocatalysis (TiO(2)) and homogeneous photocatalysis with photo-Fenton was observed. The influence of TiO(2) concentration (200 or 500 mg/L) and also of combining TiO(2) with H(2)O(2) or Na(2)S(2)O(8) on heterogeneous photocatalysis was evaluated. Heterogeneous photocatalysis with TiO(2), TiO(2)/H(2)O(2) and TiO(2)/S(2)O(8)(2-) is revealed to be inefficient in removing TOC, originating TOC degradation of 10%, 11% and 25%, respectively, at best. However, photo-Fenton experiments led to 46% TOC degradation in simulated wastewater prepared with diluted wine (WV) and 93% in wastewater prepared with diluted grape juice (WG), and if ethanol is previously eliminated from mixed wine and grape juice wastewater (WW) by air stripping, it removes 96% of TOC. Furthermore, toxicity decreases during the photo-Fenton reaction very significantly from 48% to 28%. At the same time, total polyphenols decrease 92%, improving wastewater biodegradability.

Experimental design approach to the optimization of ultrasonic degradation of alachlor and enhancement of treated water biodegradability.

This work presents the application of experimental design for the ultrasonic degradation of alachlor which is pesticide classified as priority substance by the European Commission within the scope of the Water Framework Directive. The effect of electrical power (20-80W), pH (3-10) and substrate concentration (10-50mgL(-1)) was evaluated. For a confidential level of 90%, pH showed a low effect on the initial degradation rate of alachlor; whereas electrical power, pollutant concentration and the interaction of these two parameters were significant. A reduced model taking into account the significant variables and interactions between variables has shown a good correlation with the experimental results. Additional experiments conducted in natural and deionised water indicated that the alachlor degradation by ultrasound is practically unaffected by the presence of potential *OH radical scavengers: bicarbonate, sulphate, chloride and oxalic acid. In both cases, alachlor was readily eliminated ( approximately 75min). However, after 4h of treatment only 20% of the initial TOC was removed, showing that alachlor by-products are recalcitrant to the ultrasonic action. Biodegradability test (BOD5/COD) carried out during the course of the treatment indicated that the ultrasonic system noticeably increases the biodegradability of the initial solution.

Coupled photo-Fenton-biological system: effect of the Fenton parameters such as residual H2O2, Fe2+ and pH on the efficiency of biological process.

The aim of this research work is to evaluate the performance of packed-bed bioreactors under typical conditions of photo-Fenton treatment (residual iron, residual hydrogen peroxide, acidic pH). The target pollutant selected was 4-Chlorophenol which is included in the list of Priority Substances (Decision No 2455/2001/EC) in the field of water policy and amending Directive 2000/60/EC. It was found that the biological process operated correctly during eight days when the pH was in the range of 3.5-7. In the same way, the presence of hydrogen peroxide in similar concentrations to that used in the photo-Fenton process was not negative on the biological activity. On the other hand, the presence of residual iron in the biological treatment could not be observed as a consequence of the optimal dosage used for the photo-Fenton treatment. The iron dosage is still low enough to ensure non-inhibitory effects. The results obtained in this study can provide a practical knowledge for a real application.

Factorial experimental design of winery wastewaters treatment by heterogeneous photo-Fenton process.

Winery wastewaters are difficult to treat by conventional biological processes because they are seasonal and experience a substantial flow variations. Photocatalytic advanced oxidation is a promising technology for wastewaters containing high amounts of organic matter. In this work, the photo-Fenton process in heterogeneous phase is presented as an alternative methodology for the treatment of winery wastewaters. As a consequence of the great number of existing variables, an experimental design methodology has been used in order to study the influence and interaction of various variables and to obtain a reduced empirical model which describes the organic matter degradation process. Applying photo-Fenton treatment in heterogeneous phase under energetic conditions for synthetic samples simulating winery wastewaters results in purification levels of up to 50% (measured as total organic carbon). Different reduced models are obtained and their utilization depends mainly on the degree of degradation of organic matter required.

Characterization and photo-Fenton treatment of used tires leachate.

In this study the leachates derived from used tires were firstly characterized by means of the evaluation of their organic matter content. The leachate from tire powder presented a COD value of 508 mg O(2) l(-1) and a TOC of 214 mg Cl (-1). The main identified organic substances were constituents of the rubber structure: benzothiazole derivatives, phthalates, phenolic derivatives, hydrocarbons and fatty acids. The application of photo-Fenton treatment was investigated in order to obtain the maximum organic matter removal. When a solar chamber as light source was used (light intensity=500 Wm(-2)), the best operational conditions were the following: [H(2)O(2)]=3703 mg l(-1), [Fe(2+)]=92.1 mg l(-1), initial pH 2.7-3.0, reaction time=100 min. After the photo-Fenton treatment at optimum conditions, the reached COD and TOC reduction was 64% and 48%, respectively. The main initial organic substances were eliminated after the reaction and no significant by-products were identified. A complementary treatment consisted of coagulation-flocculation carried out with FeCl(3) x 6H(2)O at pH 12 produced a maximum organic matter removal of 43% as COD and 39% as TOC. A combination of photo-Fenton followed by coagulation-flocculation enhanced the organic matter removal: a reduction of 77% of COD and 64% of TOC was attained.