A novel approach to interpret quasi-collimated beam results to support design and scale-up of vacuum UV based AOPs.

UV-C at 254 nm and vacuum UV (VUV) at 185 nm are the two major emission lines of a low-pressure mercury lamp. Upon absorption of VUV photons, water molecules and selected inorganic anions generate hydroxyl (HO.) and other redox radicals, both capable of degrading organic micropollutants (OMPs), thereby offering the opportunity to reduce H2O2 and energy consumption in UV-based advanced oxidation process (AOP). To be successfully scaled-up, the dual-wavelength VUV+UV/H2O2 AOP requires laboratory-scale experiments to establish design criteria. The figures of merit typically used for reporting and interpreting quasi-collimated beam results for UV-based AOPs (time, dose, absorbed energy and EEO) are insufficient and inaccurate when employed for dual-wavelength AOP such as the VUV+UV/H2O2 AOP, and do not support system scale-up. In this study, we introduce a novel figure of merit, useful absorbed energy (uAE), defined as fraction of absorbed energy that results in the generation of oxidative radicals. Here, results of quasi-collimated beam VUV+UV/H2O2 AOP experiments on four different water matrices are used to introduce 2D plots that employ both uAEUV and uAEVUV as a novel method to represent laboratory-scale experiments of VUV+UV/H2O2 AOP and demonstrate how the 2D plots sufficiently support scale-up of the AOP.

The impact of wastewater matrix on the degradation of pharmaceutically active compounds by oxidation processes including ultraviolet radiation and sulfate radicals.

Ultraviolet radiation (UV)-activated peroxydisulfate (PDS) and peroxymonosulfate (PMS) advanced oxidation processes were examined for their capacity to remove nine pharmaceutically active compounds (PhACs) from secondary effluent. The effect of operational parameters (initial oxidant concentration, UV exposure time, pH, common coexisting anions and effluent organic matter (EfOM)) on UV/PDS and UV/PMS treatment efficiency was investigated in a collimated beam device housing a low-pressure mercury UV lamp emitting light at 253.7 nm. Both AOPs achieved high removals (>90%) when applied to pure water. Under otherwise similar conditions the removal percentage fell by 20-30% due to the scavenging of effluent organic matter (EfOM) in secondary effluent. Finally, eliminating EfOM but maintaining the inorganic composition, the radical scavenging effect was reduced and 98.3% and 85.6% average removals were obtained by UV/PDS and UV/PMS, respectively. Increasing pH improved degradation of several PhACs containing amine groups. Higher oxidant dosages created only a significant benefit in UV/PDS. The chloride anion produced a negligible effect on both processes, while higher nitrate concentrations increased removal percentage but did not affect degradation rate constants. Finally and surprisingly, the addition of bicarbonate had the strongest positive impact on the degradation kinetics observed, even stronger than the elimination of EfOM from secondary effluent.

Evaluation of emerging contaminants in a drinking water treatment plant using electrodialysis reversal technology.

Emerging contaminants (EC) have gained much attention with globally increasing consumption and detection in aquatic ecosystems during the last two decades from ng/L to lower ug/L. The aim of this study was to evaluate the occurrence and removal of pharmaceutically active compounds (PhACs), endocrine disrupting chemicals (EDCs) and related compounds in a Drinking Water Treatment Plant (DWTP) treating raw water from the Mediterranean Llobregat River. The DWTP combined conventional treatment steps with the world's largest electrodialysis reversal (EDR) facility. 49 different PhACs, EDCs and related compounds were found above their limit of quantification in the influent of the DWTP, summing up to a total concentration of ECs between 1600-4200 ng/L. As expected, oxidation using chlorine dioxide and granular activated carbon filters were the most efficient technologies for EC removal. However, despite the low concentration detected in the influent of the EDR process, it was also possible to demonstrate that this process partially removed ionized compounds, thereby constituting an additional barrier against EC pollution in the product. In the product of the EDR system, only 18 out of 49 compounds were quantifiable in at least one of the four experimental campaigns, showing in all cases removals higher than 65% and often beyond 90% for the overall DWTP process.

Removal of micropollutants during tertiary wastewater treatment by biofiltration: Role of nitrifiers and removal mechanisms.

The objective of this study was to determine the extent to which a suite of organic micropollutants (MPs) can be removed by biological filtration and the role of bioavailability and ammonia oxidizing microorganisms (AOMs) in the biodegradation process. During approximately one year, laboratory-scale columns with 8 min empty bed contact time (EBCT) and packed with anthracite as filter media were used for treating a tertiary effluent spiked with a broad range of MPs at a target concentration of 2 µg L(-1). In parallel columns, aerobic biomass growth was inhibited by using either the biocide sodium azide (500 mg L(-1) NaN3) or allylthiourea (5 mg L(-1) ATU), specifically inhibiting nitrifying bacteria. Once the biomass had colonized the media, around 15% of the dissolved organic carbon (DOC) contained in the untreated tertiary effluent was removed by non-inhibited columns. The removal of several MPs increased over time indicating the relevance of biological activity for the removal of MPs, while the negative control, the NaN3 inhibited column, showed no significant removal. Out of 33 MPs, 19 were recalcitrant (<25%) to biodegradation under aerobic conditions with the others exhibiting a diverse range of removal efficiency up to 95%. Through inhibition by ATU it was shown that nitrifying bacteria were clearly having a role in the degradation of several MPs, whereas the removal of other MPs was not affected by the presence of the nitrification inhibitor. A relationship between the qualitative assessment of sorption of MPs on granular activated carbon (GAC) and their removal efficiency by biodegradation on anthracite was observed. This result suggested that the affinity of the MPs for GAC media could be a useful indicator of the bioavailability of compounds during biofiltration on anthracite.

Sewage pollution in urban stormwater runoff as evident from the widespread presence of multiple microbial and chemical source tracking markers.

The concurrence of human sewage contamination in urban stormwater runoff (n=23) from six urban catchments across Australia was assessed by using both microbial source tracking (MST) and chemical source tracking (CST) markers. Out of 23 stormwater samples human adenovirus (HAv), human polyomavirus (HPv) and the sewage-associated markers; Methanobrevibacter smithii nifH and Bacteroides HF183 were detected in 91%, 56%, 43% and 96% of samples, respectively. Similarly, CST markers paracetamol (87%), salicylic acid (78%) acesulfame (96%) and caffeine (91%) were frequently detected. Twenty one samples (91%) were positive for six to eight sewage related MST and CST markers and remaining two samples were positive for five and four markers, respectively. A very good consensus (>91%) observed between the concurrence of the HF183, HAv, acesulfame and caffeine suggests good predictability of the presence of HAv in samples positive for one of the three markers. High prevalence of HAv (91%) also suggests that other enteric viruses may also be present in the stormwater samples which may pose significant health risks. This study underscores the benefits of employing a set of MST and CST markers which could include monitoring for HF183, adenovirus, caffeine and paracetamol to accurately detect human sewage contamination along with credible information on the presence of human enteric viruses, which could be used for more reliable public health risk assessments. Based on the results obtained in this study, it is recommended that some degree of treatment of captured stormwater would be required if it were to be used for non-potable purposes.

Microbial community analysis of fouled reverse osmosis membranes used in water recycling.

Biofouling on RO membranes has major cost implications in water reclamation. In this study membranes and water samples were collected from a RO pilot-plant operated on two sites to study the differences in microbial communities in order to develop a better understanding of the biofouling. For the two sites studied, the examination of the front membrane of the first stage and the tail membrane of the second stage of the RO train using 16S rRNA gene-based molecular technique showed that bacteria were similar on both stages and no significant effect of the membrane location within the RO train on the biofilm development could be discerned. However, the comparison of the identified bacteria from membrane samples between the two sites showed that each site is specific, leading to a different composition of microbial communities. The different nutrient concentrations in the RO feed water due to the different biological pre-treatments are one potential explanation for the observed differences in the microbial communities. Seasonal variations also play a major role in the development of microbial communities as shown by the significant differences observed between the communities measured in the samples in winter and summer on the second site. The results did not show similarity between the species identified on the RO membranes and in the feed water. Hence, the relationship of microbial community between the water generated during the pre-treatment process and RO membranes is not obvious. From this study, results showed that there is an actual need to investigate the development of microbial communities on membrane surface in real conditions in order to suggest tailored solutions for biofouling control and removal.

Impact of effluent organic matter on low-pressure membrane fouling in tertiary treatment.

This study aims at comparing low-pressure membrane fouling obtained with two different secondary effluents at bench and pilot-scale based on the determination of two fouling indices: the total fouling index (TFI) and the hydraulically irreversible fouling index (HIFI). The main objective was to investigate if simpler and less costly bench-scale experimentation can substitute for pilot-scale trials when assessing the fouling potential of secondary effluent in large scale membrane filtration plants producing recycled water. Absolute values for specific flux and total fouling index for the bench-scale system were higher than those determined from pilot-scale, nevertheless a statistically significant correlation (r(2) = 0.63, α = 0.1) was obtained for the total fouling index at both scales. On the contrary no such correlation was found for the hydraulically irreversible fouling index. Advanced water characterization tools such as excitation-emission matrix fluorescence spectroscopy (EEM) and liquid chromatography with organic carbon detection (LC-OCD) were used for the characterization of foulants. On the basis of statistical analysis, biopolymers and humic substances were found to be the major contribution to total fouling (r(2) = 0.95 and r(2) = 0.88, respectively). Adsorption of the low molecular weight neutral compounds to the membrane was attributed to hydraulically irreversible fouling (r(2) = 0.67).

Ozonation and biological activated carbon filtration of wastewater treatment plant effluents.

This study investigates the fate of trace organic chemicals (TrOCs) in three full-scale reclamation plants using ozonation followed by biological activated carbon (BAC) filtration to treat wastewater treatment plant effluents. Chemical analysis was used to quantify a wide range of TrOCs and combined with bioanalytical tools to assess non-specific toxicity (Microtox assay) and estrogenicity (E-SCREEN assay). Limited dissolved organic carbon (DOC) removal (<10%) was observed in the ozonation stages showing that oxidation leads to the formation of transformation products rather than mineralization. The quantified TrOCs were removed to a degree highly dependent on the compounds' structures and the specific ozone dose (mg(O3) mg(DOC)(-1)). Non-specific toxicity was reduced by 31-39%, demonstrating that the mixture of remaining parent compounds and their transformation products as well as newly formed oxidation by-products had an overall lower toxic potential than the mixture of parent compounds. Estrogenicity was reduced by more than 87% indicating that the transformation products of the estrogenic chemicals lost their specific toxicity potential. The subsequent BAC filtration removed between 20 and 50% of the DOC depending on the plant configuration, likely due to biodegradation of organic matter. The filtration was also able to reduce the concentrations of most of the remaining TrOCs by up to 99%, and reduce non-specific toxicity by 33-54%. Overall, the combination of ozonation and BAC filtration can achieve removals of 50% for DOC and more than 90% for a wide range of TrOCs as well as a reduction of 70% of non-specific toxicity and more than 95% of estrogenicity. This process combination is therefore suggested as an effective barrier to reduce the discharge of TrOCs into the environment or their presence in water recycling schemes.

Occurrence of N-nitrosodimethylamine precursors in wastewater treatment plant effluent and their fate during ultrafiltration-reverse osmosis membrane treatment.

The formation of N-nitrosodimethylamine (NDMA) is of major concern among wastewater recycling utilities practicing disinfection with chloramines. The NDMA formation potential (FP) test is a simple and straightforward method to evaluate NDMA precursor concentrations in waters. In this paper we show the NDMA FP results of a range of tertiary wastewater treatment plants that are also the source for production of recycled water using an Ultrafiltration - Reverse Osmosis (UF-RO) membrane process. The results indicate that the NDMA FP of different source waters range from 350 to 1020±20 ng/L. The fate of these NDMA precursors was also studied across the different stages of two Advanced Water Treatment Plants (AWTP) producing recycled water. These results show that more than 98.5±0.5% of NDMA precursors are effectively removed by the Reverse Osmosis (RO) membranes used at the AWTPs. This drastically reduces any potential for re-formation of NDMA after the RO stage even if chloramines may be present (or added) there.

Solar photo-Fenton as finishing step for biological treatment of a pharmaceutical wastewater.

Remediation of pharmaceutical wastewater, containing nalidixic acid (NXA; 38 mg/L), a quinolone antibacterial agent commonly used in human and veterinary medicine, and characterized as having mainly 725 mg/L dissolved organic carbon (DOC), 3400 mg/L chemical oxygen demand, and around 4 g/L NaCl, was studied. A prior biodegradability study (Zahn-Wellens test) had demonstrated that the matrix was biodegradable after a rather long biomass adaptation period. After 4 days of treatment in an immobilized biomass reactor (IBR), 96% of the original DOC was removed by the biological treatment however, more than 50% of NXA was adsorbed on the biomass. As development of chronic toxicity in the IBR is possible after long exposure to NXA, adsorption and biomass stability during continuous exposure to NXA were studied in different cycles for one month. Afterthe biotreatment, the effluent was treated by solar photo-Fenton. Total degradation of NXA and reduction in toxicity were observed. The intermediates formed during degradation by biotreatment and subsequent photo-Fenton were studied by liquid chromatography-time-of-flight mass spectrometry.

Decontamination industrial pharmaceutical wastewater by combining solar photo-Fenton and biological treatment.

Characterization and treatment of a real pharmaceutical wastewater containing 775 mg dissolved organic carbon per liter by a solar photo-Fenton/biotreatment were studied. There were also many inorganic compounds present in the matrix. The most important chemical in this wastewater was nalidixic acid (45 mg/L), an antibiotic pertaining to the quinolone group. A Zahn-Wellens test demonstrated that the real bulk organic content of the wastewater was biodegradable, but only after long biomass adaptation; however, the nalidixic acid concentration remained constant, showing that it cannot be biodegraded. An alternative is chemical oxidation (photo-Fenton process) first to enhance biodegradability, followed by a biological treatment (Immobilized Biomass Reactor--IBR). In this case, two studies of photo-Fenton treatment of the real wastewater were performed, one with an excess of H2O2 (kinetic study) and another with controlled H2O2 dosing (biodegradability and toxicity studies). In the kinetic study, nalidixic acid completely disappeared after 190 min. In the other experiment with controlled H2O2, nalidixic acid degradation was complete at 66 mM of H2O2 consumed. Biodegradability and toxicity bioassays showed that photo-Fenton should be performed until total degradation of nalidixic acid before coupling a biological treatment. Analysis of the average oxidation state (AOS) demonstrated the formation of more oxidized intermediates. With this information, the photo-Fenton treatment time (190 min) and H2O2 dose (66 mM) necessary for adequate biodegradability of the wastewater could be determined. An IBR operated in batch mode was able to reduce the remaining DOC to less than 35 mg/L. Ammonium consumption and NO3- generation demonstrated that nitrification was also attained in the IBR. Overall DOC degradation efficiency of the combined photo-Fenton and biological treatment was over 95%, of which 33% correspond to the solar photochemical process and 62% to the biological treatment.

Advanced oxidation process-biological system for wastewater containing a recalcitrant pollutant.

Two advanced oxidation processes (AOPs), ozonation and photo-Fenton, combined with a pilot aerobic biological reactor at field scale were employed for the treatment of industrial non-biodegradable saline wastewater (TOC around 200 mgL(-1)) containing a biorecalcitrant compound, alpha-methylphenylglycine (MPG), at a concentration of 500 mgL(-1). Ozonation experiments were performed in a 50-L reactor with constant inlet ozone of 21.9 g m(-3). Solar photo-Fenton tests were carried out in a 75-L pilot plant made up of four compound parabolic collector (CPC) units. The catalyst concentration employed in this system was 20 mgL(-1) of Fe2+ and the H2O2 concentration was kept in the range of 200-500mgL(-1). Complete degradation of MPG was attained after 1,020 min of ozone treatment, while only 195 min were required for photo-Fenton. Samples from different stages of both AOPs were taken for Zahn-Wellens biocompatibility tests. Biodegradability enhancement of the industrial saline wastewater was confirmed (>70% biodegradability). Biodegradable compounds generated during the preliminary oxidative processes were biologically mineralised in a 170-L aerobic immobilised biomass reactor (IBR). The global efficiency of both AOP/biological combined systems was 90% removal of an initial TOC of over 500 mgL(-1).

Increased biodegradability of Ultracid in aqueous solutions with solar TiO2 photocatalysis.

A study of solar TiO(2) photocatalytic degradation of the insecticide Ultracidtrade mark, a commercial formulation containing methidathion as the active ingredient, is described. Total elimination of methidathion can be achieved in less than 2h of irradiation, although longer solar exposures are needed for complete mineralisation of the solution (7-8h). Activated sludge respirometry shows that when methidathion is eliminated, the solution is detoxified, so further irradiation does not seem necessary. A Zahn-Wellens test also indicates improved biodegradability of the treated sample after abatement of the active ingredient. Finally, analysis of the ions formed indicates that the thiophosphate moiety of the molecule is preferentially attacked in the early stages of the reaction, while the thiadiazole ring is more sluggish to the effect of TiO(2)-photocatalysis.

Partial degradation of five pesticides and an industrial pollutant by ozonation in a pilot-plant scale reactor.

Aqueous solutions of a mixture of several pesticides (alachlor, atrazine, chlorfenvinphos, diuron and isoproturon), considered PS (priority substances) by the European Commission, and an intermediate product of the pharmaceutical industry (alpha-methylphenylglycine, MPG) chosen as a model industrial pollutant, have been degraded at pilot-plant scale using ozonation. This study is part of a large research project [CADOX Project, A Coupled Advanced Oxidation-Biological Process for Recycling of Industrial Wastewater Containing Persistent Organic Contaminants, Contract No.: EVK1-CT-2002-00122, European Commission, http://www.psa.es/webeng/projects/cadox/index.html] founded by the European Union that inquires into the potential coupling between chemical and biological oxidations for the removal of toxic or non-biodegradable contaminants from water. The evolution of pollutant concentration, TOC mineralization, generation of inorganic species and consumption of O3 have been followed in order to visualize the chemical treatment effectiveness. Although complete mineralization is hard to accomplish, and large amounts of the oxidant are required to lower the organic content of the solutions, the possibility of ozonation cannot be ruled out if partial degradation is the final goal wanted. In this sense, Zahn-Wellens biodegradability tests of the ozonated MPG solutions have been performed, and the possibility of a further coupling with a secondary biological treatment for complete organic removal is envisaged.

Solar photocatalytic degradation of some hazardous water-soluble pesticides at pilot-plant scale.

The technical feasibility and performance of photocatalytic degradation of six water-soluble pesticides (cymoxanil, methomyl, oxamyl, dimethoate, pyrimethanil and telone) have been studied at pilot-plant scale in two well-defined systems which are of special interest because natural solar UV light can be used: heterogeneous photocatalysis with titanium dioxide and homogeneous photocatalysis by photo-Fenton. TiO(2) photocatalysis tests were performed in a 35L solar pilot plant with three Compound Parabolic Collectors (CPCs) under natural illumination and a 75L solar pilot plant with four CPC units was used for homogeneous photocatalysis tests. The initial pesticide concentration studied was 50 mg L(-1) and the catalyst concentrations employed were 200 mg L(-1) of TiO(2) and 20 mg L(-1) of iron. Both toxicity (Vibrio fischeri, Biofix) and biodegradability (Zahn-Wellens test) of the initial pesticide solutions were also measured. Total disappearance of the parent compounds and nearly complete mineralization were attained with all pesticides tested. Treatment time, hydrogen peroxide consumption and release of heteroatoms are discussed.

Treatment of chlorinated solvents by TiO2 photocatalysis and photo-Fenton: influence of operating conditions in a solar pilot plant.

Titanium dioxide photocatalysis (using 20 0mg l(-1) of TiO2), under aerobic and anaerobic conditions, and photo-Fenton (2 and 56 mg l(-1) iron) were applied to the treatment of different NBCS (non-biodegradable chlorinated solvents), such as dichloroethane, dichloromethane and trichloromethane dissolved in water at 50 mg l(-1). All the tests were performed in a 35-l solar pilot plant with compound parabolic collectors (CPCs) under natural illumination. The two solar treatments were compared with attention to chloride release and TOC mineralisation, as the main parameters. Photo-Fenton was found to be the more appropriate treatment for these compounds, assuming volatilisation as a drawback of photocatalytic degradation of NBCS dissolved in water. In this context, several operating parameters related to NBCS degradation, e.g., treatment time, temperature, hydrogen peroxide consumption and volatility of parent compounds are discussed. The correct choice of operating conditions can very often diminish the problem of volatilisation during treatment.