Degradation of estriol (E3) and transformation pathways after applying photochemical removal processes in natural surface water.

Steroidal hormones such as estriol (E3), are resistant to biodegradation; hence their removal by conventional treatment systems (aerobic and anaerobic) facilities is limited. These substances are detected in surface water, and present risks to the aquatic ecosystem and humans via potential biological activity. Photochemical treatments can be used to remove E3; however, just a few studies have analyzed the kinetics, intermediates, and E3 degradation pathways in natural surface water. In this study, the behavior of E3 under ultraviolet irradiation associated with H2O2, O3 or TiO2 was investigated to determine the degradation potential and the transformation pathways in reactions performed with a natural surface water sample. E3 degradation kinetics (200 ppb) fitted well to the pseudo-first-order kinetics model, with kinetic constant k in the following order: kUV/O3 > kUV/TiO2 > kUV/H2O2 > kUV. The mechanism of degradation using different advanced oxidative processes seemed to be similar and 12 transformation byproducts were identified, with 11 of them being reported here for the first time. The byproducts could be formed by the opening of the aromatic ring and addition of a hydroxyl radical. A possible route of E3 degradation was proposed based on the byproducts identified, and some of the byproducts presented chronic toxicity to aquatic organisms, demonstrating the risks of exposure.

The removal and degradation of pharmaceutical compounds during membrane bioreactor treatment.

Pharmaceutical compounds such as non-steroidal anti-inflammatory drugs (NSAIDs) and antibiotics have been detected in sewage treatment plant (STP) effluents, surface and ground water and even in drinking water all over the world, and therefore have developed as compounds of concern. Membrane bioreactor (MBR) treatment has gained significant popularity as an advanced wastewater treatment technology and might be effective for an advanced removal of these pollutants. This paper evaluates the treatment of wastewater containing three NSAIDs (acetaminophen, ketoprofen and naproxen) and three antibiotics (roxithromycin, sulfamethoxazole and trimethoprim) performed in two MBRs with sludge retention times (SRTs) of 15 (MBR-15) and 30 (MBR-30) days over a period of four weeks. It was observed that NSAIDs were removed with higher efficiencies than the antibiotics for both MBRs, and the MBR-30 presented higher removal efficiencies for all the compounds than obtained by MBR-15. Removal rates ranged from 55% (sulfamethoxazole) up to 100% (acetaminophen, ketoprofen). Besides mineralisation biological transformation products of ketoprofen and naproxen produced by wastewater biocoenosis were identified in both MBR permeates using liquid chromatography coupled with mass spectrometry (LC-MS). The results indicated the importance of investigating the environmental fate of pharmaceuticals and their transformation products reaching the environment.

Evaluation of hybrid treatments to produce high quality reuse water.

Four tertiary hybrid treatments to produce high quality reused water, fulfilling Brazilian drinking water regulations, from a slaughterhouse's secondary treated effluent were evaluated. The pilot plant with a capacity of 500 L h(-1) was set up and consisted of these stages: pre-filtration system (cartridge filter 50 micron, activated carbon filter, cartridge filter 10 micron), oxidation (H2O2) or second filtration (ceramic filter, UF) followed by UV radiation (90 L h(-1)). The best combination was T4: pre-filtration followed by H2O2 addition and UV radiation (AOP H2O2/UV). Disinfection kinetics by T4 followed pseudo first-order kinetics: k(T4) = 0.00943 s(-1) or 0.00101 cm2 mJ(-1). Three different zones (A, B, C) were observed in the UV254 degradation kinetics (pseudo-first order kinetics): k' decreased over time (k'(A) > k'(B) > k'(C)).

Biological wastewater treatment followed by physicochemical treatment for the removal of fluorinated surfactants.

Perfluorinated surfactants (PFS) have become compounds of high concern during the last decade. While "conventional surfactants" are degraded to a great extent in the biological wastewater treatment process, partly or perfluorinated surfactants are not only stable against biodegradation but also against oxidizing agents, they even resist OH-radical attacks. Our objectives were to eliminate the fluorinated surfactants perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) by adsorption, separation or degradation with a balance of precursor compounds and follow-up of degradation products. Therefore, municipal wastewater was spiked with these fluorinated surfactants before membrane bioreactor (MBR) treatment-applying microfiltration membranes--was performed and before permeates were treated using ozone (O3) or different advanced oxidation treatment (AOP) techniques. O3 or hydrogen peroxide (H2O2), both in combination with UV radiation or in combination with catalysts, was applied. Removal by adsorption or membrane separation as well as degradation were monitored by substance specific determination and identification. High resolution mass spectrometry after high performance liquid chromatography (HPLC/HRMS and -MS(n)) was used for analysis. Contact to Teflon and/or glass during all analytical procedures was avoided.

Tertiary treatment of slaughterhouse effluent: degradation kinetics applying UV radiation or H2O2/UV.

In some Brazilian regions, surface water has become scarce, e.g. semi arid climate areas and densely populated and industrial areas, where water over-exploitation and/or fluvial pollution has been more common. Advanced oxidative processes (AOP) provide treated water as a source of reuse water even with the characteristics of drinking water enabling water reuse practices also in food industries. The secondary wastewater of a slaughterhouse was the water source for a tertiary treatment study evaluating the kinetics of the photo-induced degradation of color and UV254 under UV radiation with and without the addition of H2O2. The proximity of the k' values of color and UV254 degradation by UV indicates that the compounds responsible for color may be the same content measured by UV254. The H2O2/UV treatment was 5.2 times faster than simple UV in removing aromatic compounds. The degradation kinetics of aromatic compounds in both treatments followed a pseudo-first order law. The pseudo-first order constant for H2O2/UV and UV treatments were kUV254'=0.0306 min(-1) and kUV254'=0.0056 min(-1), respectively.

Generation of endocrine disruptor compounds during ozone treatment of tannery wastewater confirmed by biological effect analysis and substance specific analysis.

Ozone (O3) with its high oxidation potential was used to degrade or eliminate pollutants contained in tannery wastewater when applying different pHs and quantities of O3. Our objective was a chemical degradation by O3 to achieve an enhancement of biodegradability, with a parallel decrease in toxicity. Conventional analyses and bioassays beside substance specific analyses were performed to clear-up the behaviour of wastewater content from tanning process. The results demonstrate that the dominant organic pollutants were chemically degraded by oxidation as the chemical and biochemical oxygen demand (COD and BOD) prove, while changes in carbon content monitored by total or dissolved organic carbon content (TOC or DOC) were only marginal. Vibrio fischeri and Daphnia magna toxicity testing performed in parallel proved a decrease in toxicity after O3-treatment, while the estrogenic activity determined by enzyme-linked receptor assay (ELRA), however, proved an increase of endocrine disruptor compounds (EDC). Results could be explained by substance-specific analyses using gas chromatography (GC-MS) and liquid chromatography/mass spectrometry (LC-MS). From GC-MS analysis the elimination of non-polar compounds could be recognized, whereas the oxidative conversion led to an increase of EDC compounds, which qualitatively could be identified by LC-MS as nonylphenol ethoxylate (NPEO) degradation products: short chain NPEOs, nonylphenol carboxylates (NPECs) and nonylphenol (NP).

Enhanced ozonation degradation of petroleum refinery wastewater in the presence of oxide nanocatalysts.

The catalytic activity of Mn2O3, FeOOH and CeO2 nanoparticles was evaluated in the treatment of a synthetic petroleum refinery wastewater (SPRW) using O3 in a discontinuous reactor at 25°C and pH 5.5. The mineralization and partial chemical oxidation rates of SPRW using these metal oxides are in the same order of magnitude, and the catalytic activity in the mineralization of SPRW decreased in the order Mn2O3 > CeO2 > FeOOH. The mineralized fraction progressively increased with time in the catalytic process while in the non-catalytic process it remained constant. The effect of the operational conditions on the mineralization and partial chemical oxidation rates using Mn2O3 was investigated in detail. The mineralization rate was found to be lower than the partial oxidation rate due to the formation of partially oxidized by-products, and this is dependent on the solids dosage and pH. An investigation of the mechanism demonstrated that the enhancement effect could be attributed to the introduction of the manganese oxide nanoparticles, which could promote the utilization of O3 and/or enhance the formation of free radicals (•OH, •O2H and •O2-) on the solid surface and further accelerate the degradation of the organic compounds present in the wastewater.

Applicability of Fenton and H2O2/UV reactions in the treatment of tannery wastewaters.

In this paper we evaluated the H2O2/UV and the Fenton's oxidation processes for the treatment of tannery wastewater under different experimental conditions. Efficiencies were judged by the amounts of organic substances degraded or eliminated under these treatment techniques. Daphnia magna and Vibrio fischeri were used to monitor toxicity. Organic compounds contained in the untreated and treated tannery wastewater were determined and identified using substance specific techniques. Gas chromatography-mass spectrometry (GC-MS) in positive electron impact (EI(+)) mode was applied to determine volatile organics. Atmospheric pressure ionization (API) mass (MS) and tandem mass spectrometry (MS-MS) coupled with flow injection analysis (FIA) or liquid chromatography (LC) were used to detect or identify polar organic pollutants. The experimental results indicated that both oxidation processes--H2O2/UV at pH 3 and Fenton at pH 3.5--are able to reduce TOC content by mineralisation of the organic compounds.

Elucidation of the behavior of tannery wastewater under advanced oxidation conditions.

Diverse advanced oxidation process (AOP) techniques applying UV, TiO2/UV, O3 and O3/UV were used to degrade pollutants contained in tannery wastewater. The total mineralization of these pollutants is desirable, but it is quite energy consuming and sometimes impossible. Therefore the objective was to achieve an enhancement of biodegradability, preferentially with a decrease in toxicity in parallel. This work demonstrates that the dominant pollutants were chemically degraded by oxidation, while changes in carbon content were only marginal. These results were obtained monitoring the total organic carbon content (TOC), chemical and biochemical oxygen demand (COD and BOD), and substance-specific pollutant content by application of gas chromatography/mass spectrometry (GC-MS) and liquid chromatography/mass spectrometry (LC-MS). Daphnia magna toxicity testing performed in parallel proved a decrease in toxicity after AOP treatment of the tannery wastewater.

Comparison of different advanced oxidation process to reduce toxicity and mineralisation of tannery wastewater.

Many organic compounds contained in wastewater are resistant to conventional chemical and/or biological treatment. Because of this reason different degradation techniques are studied as an alternative to biological and classical physico-chemical processes. Advanced Oxidation Processes (AOPs) probably have developed to become the best options in the near future. AOP while making use of different reaction systems, are all characterised by the same chemical feature: production of OH radicals (*OH). The versatility of AOPs is also enhanced by the fact that they offer different possibilities for OH radical production, thus allowing them to conform to specific treatment requirements. The main problem with AOPs is their high cost. The application of solar technologies to these processes could help to diminish that problem by reducing the energy consumption required for generating UV radiation. In this work, different AOPs (O3, TiO2/UV, Fenton and H2O2/UV) were examined to treat tannery wastewater or as a pre-treatment step for improving the biodegradation of tannery wastewater, at different pH and dosage of the chemicals. Under certain circumstances retardation in biodegradation and/or an increase in toxicity may be observed within these treatment steps. Two different bioassays (Daphnia magna and Vibrio fischeri) have been used for testing the progress of toxicity during the treatment. In parallel other objectives were to analyse and identify organic compounds present in the untreated wastewater and arising degradation products in AOP treated wastewater samples. For this purpose substance specific techniques, e.g., gas chromatography-mass spectrometry (GC-MS) in positive electron impact (El(+)) mode and atmospheric pressure ionisation (API) in combination with flow injection analysis (FIA) or liquid chromatography-mass and tandem mass spectrometry (LC-MS or LC-MS-MS) were performed.