Antimicrobial Effectiveness of Innovative Photocatalysts: A Review.

Waterborne pathogens represent one of the most widespread environmental concerns. Conventional disinfection methods, including chlorination and UV, pose several operational and environmental problems; namely, formation of potentially hazardous disinfection by-products (DBPs) and high energy consumption. Therefore, there is high demand for effective, low-cost disinfection treatments. Among advanced oxidation processes, the photocatalytic process, a form of green technology, is becoming increasingly attractive. A systematic review was carried out on the synthesis, characterization, toxicity, and antimicrobial performance of innovative engineered photocatalysts. In recent decades, various engineered photocatalysts have been developed to overcome the limits of conventional photocatalysts using different synthesis methods, and these are discussed together with the main parameters influencing the process behaviors. The potential environmental risks of engineered photocatalysts are also addressed, considering the toxicity effects presented in the literature.

Antibiotic resistance genes in treated wastewater and in the receiving water bodies: A pan-European survey of urban settings.

There is increasing public concern regarding the fate of antibiotic resistance genes (ARGs) during wastewater treatment, their persistence during the treatment process and their potential impacts on the receiving water bodies. In this study, we used quantitative PCR (qPCR) to determine the abundance of nine ARGs and a class 1 integron associated integrase gene in 16 wastewater treatment plant (WWTP) effluents from ten different European countries. In order to assess the impact on the receiving water bodies, gene abundances in the latter were also analysed. Six out of the nine ARGs analysed were detected in all effluent and river water samples. Among the quantified genes, intI1 and sul1 were the most abundant. Our results demonstrate that European WWTP contribute to the enrichment of the resistome in the receiving water bodies with the particular impact being dependent on the effluent load and local hydrological conditions. The ARGs concentrations in WWTP effluents were found to be inversely correlated to the number of implemented biological treatment steps, indicating a possible option for WWTP management. Furthermore, this study has identified blaOXA-58 as a possible resistance gene for future studies investigating the impact of WWTPs on their receiving water.

Chloride or sulfate? Consequences for ozonation of textile wastewater.

Ozonation of chloride-rich textile wastewater is a common pretreatment practice in order to increase biodegradability and therefore meet the discharge limits. This study is the first to investigate ozone-chloride/bromide interactions and formation of hazardous adsorbable organic halogens (AOX) in real textile wastewater. Initially effect of ozonation on chloride-rich real textile wastewater samples were investigated for adsorbable organic halogens (AOX) formation, biodegradability and toxicity. After 15 min of ozonation, maximum levels of chlorine/bromine generation (0.3 mg/l) and AOX formation (399 mg/l) were reached. OUR and SOUR levels both increased by approximately 58%. Daphnia magna toxicity peaked at 100% for 10 min ozonated sample. Considering adverse effects of ozonation on chloride-rich textile industry effluents, we proposed replacement of NaCl with Na2SO4. Comparative ozonation experiments were carried out for both chloride and sulfate containing synthetic dyeing wastewater samples. Results showed that use of sulfate in reactive dyeing increased biodegradability and decreased acute toxicity. Although sulfate is preferred over chloride for more effective dyeing performance, the switch has been hampered due to sodium sulfate's higher unit cost. However, consideration of indirect costs such as contributions to biodegradability, toxicity, water and salt recovery shall facilitate textile industry's switch from chloride to sulfate.

Degradation of antibiotic ampicillin on boron-doped diamond anode using the combined electrochemical oxidation - Sodium persulfate process.

In this work, the electrochemical oxidation of antibiotic ampicillin (AMP) on a boron-doped diamond anode in the presence of sodium persulfate (SPS) was investigated (EO/SPS process). Experiments were conducted at AMP concentrations between 0.8 and 3 mg/L, SPS concentrations between 100 and 500 mg/L, current densities between 5 and 110 mA/cm2, in three water matrices (ultrapure water, bottled water and secondary treated wastewater), using 0.1 M Na2SO4 as the supporting electrolyte. AMP degradation follows a pseudo-first order kinetic expression with the apparent rate constant increasing with (i) increasing SPS concentration (from 0.08 min-1 to 0.36 min-1 at 0 and 500 mg/L SPS, respectively, 1.1 mg/L AMP, 25 mA/cm2), (ii) increasing current (from 0.08 min-1 to 0.6 min-1 at 5 and 110 mA/cm2, respectively, 1.1 mg/L AMP, 250 mg/L SPS), and (iii) decreasing AMP concentration (from 0.16 min-1 to 0.31 min-1 at 3 and 0.8 mg/L, respectively, 250 mg/L SPS, 25 mA/cm2). The presence of various anions (mainly bicarbonates) in bottled water did not impact AMP degradation. The observed kinetic constant decreased by 40% in the presence of 10 mg/L humic acid. On the other hand, process efficiency was enhanced almost 3.5 times in secondary effluent due to the electrogeneration of active chlorine species that promote indirect oxidation reactions in the bulk solution. The efficacy of the EO/SPS process was compared to and found to be considerably greater than a process where SPS was activated by simulated solar irradiation at an intensity of 7.3 × 10-7 E/(L.s) (SLR/SPS process). Coupling the two processes (EO/SLR/SPS) resulted in a cumulative, in terms of AMP degradation, effect. The combined process was tested for AMP degradation, mineralization and inhibition to Vibrio fischeri in wastewater; fast AMP removal was accompanied by low mineralization and incomplete toxicity removal.

Removal of antibiotics in a parallel-plate thin-film-photocatalytic reactor: Process modeling and evolution of transformation by-products and toxicity.

Photocatalytic degradation of sulfamethoxazole (SMX) antibiotic has been studied under recycling batch and homogeneous flow conditions in a thin-film coated immobilized system namely parallel-plate (PPL) reactor. Experimentally designed, statistically evaluated with a factorial design (FD) approach with intent to provide a mathematical model takes into account the parameters influencing process performance. Initial antibiotic concentration, UV energy level, irradiated surface area, water matrix (ultrapure and secondary treated wastewater) and time, were defined as model parameters. A full of 25 experimental design was consisted of 32 random experiments. PPL reactor test experiments were carried out in order to set boundary levels for hydraulic, volumetric and defined defined process parameters. TTIP based thin-film with polyethylene glycol+TiO2 additives were fabricated according to pre-described methodology. Antibiotic degradation was monitored by High Performance Liquid Chromatography analysis while the degradation products were specified by LC-TOF-MS analysis. Acute toxicity of untreated and treated SMX solutions was tested by standard Daphnia magna method. Based on the obtained mathematical model, the response of the immobilized PC system is described with a polynomial equation. The statistically significant positive effects are initial SMX concentration, process time and the combined effect of both, while combined effect of water matrix and irradiated surface area displays an adverse effect on the rate of antibiotic degradation by photocatalytic oxidation. Process efficiency and the validity of the acquired mathematical model was also verified for levofloxacin and cefaclor antibiotics. Immobilized PC degradation in PPL reactor configuration was found capable of providing reduced effluent toxicity by simultaneous degradation of SMX parent compound and TBPs.

Polymer functionalized nanocomposites for metals removal from water and wastewater: An overview.

Pollution by metal and metalloid ions is one of the most widespread environmental concerns. They are non-biodegradable, and, generally, present high water solubility facilitating their environmental mobilisation interacting with abiotic and biotic components such as adsorption onto natural colloids or even accumulation by living organisms, thus, threatening human health and ecosystems. Therefore, there is a high demand for effective removal treatments of heavy metals, making the application of adsorption materials such as polymer-functionalized nanocomposites (PFNCs), increasingly attractive. PFNCs retain the inherent remarkable surface properties of nanoparticles, while the polymeric support materials provide high stability and processability. These nanoparticle-matrix materials are of great interest for metals and metalloids removal thanks to the functional groups of the polymeric matrixes that provide specific bindings to target pollutants. This review discusses PFNCs synthesis, characterization and performance in adsorption processes as well as the potential environmental risks and perspectives.

Chemical and biological treatment technologies for leather tannery chemicals and wastewaters: a review.

Although the leather tanning industry is known to be one of the leading economic sectors in many countries, there has been an increasing environmental concern regarding the release of various recalcitrant pollutants in tannery wastewater. It has been shown that biological processes are presently known as the most environmental friendly but inefficient for removal of recalcitrant organics and micro-pollutants in tannery wastewater. Hence emerging technologies such as advanced oxidation processes and membrane processes have been attempted as integrative to biological treatment for this sense. This paper, as the-state-of-the-art, attempts to revise the over world trends of treatment technologies and advances for pollution prevention from tannery chemicals and wastewater. It can be elucidated that according to less extent advances in wastewater minimization as well as in leather production technology and chemicals substitution, biological and chemical treatment processes have been progressively studied. However, there has not been a full scale application yet of those emerging technologies using advanced oxidation although some of them proved good achievements to remove xenobiotics present in tannery wastewater. It can be noted that advanced oxidation technologies integrated with biological processes will remain in the agenda of the decision makers and water sector to apply the best prevention solution for the future tanneries.

Pharmaceutical residues in environmental waters and wastewater: current state of knowledge and future research.

Pollution from pharmaceuticals in the aquatic environment is now recognized as an environmental concern in many countries. This has led to the creation of an extensive area of research, including among others: their chemical identification and quantification; elucidation of transformation pathways when present in wastewater-treatment plants or in environmental matrices; assessment of their potential biological effects; and development and application of advanced treatment processes for their removal and/or mineralization. Pharmaceuticals are a unique category of pollutants, because of their special characteristics, and their behavior and fate cannot be simulated with other chemical organic contaminants. Over the last decade the scientific community has embraced research in this specific field and the outcome has been immense. This was facilitated by advances in chromatographic techniques and relevant biological assays. Despite this, a number of unanswered questions exist and still there is much room for development and work towards a more solid understanding of the actual consequences of the release of pharmaceuticals in the environment. This review tries to present part of the knowledge that is currently available with regard to the occurrence of pharmaceutical residues in aquatic matrices, the progress made during the last several years on identification of such compounds down to trace levels, and of new, previously unidentified, pharmaceuticals such as illicit drugs, metabolites, and photo-products. It also tries to discuss the main recent findings in respect of the capacity of various treatment technologies to remove these contaminants and to highlight some of the adverse effects that may be related to their ubiquitous existence. Finally, socioeconomic measures that may be able to hinder the introduction of such compounds into the environment are briefly discussed.

Occurrence patterns of pharmaceuticals in water and wastewater environments.

The occurrence of pharmaceuticals and their metabolites and transformation products in the environment is becoming a matter of concern, because these compounds, which may have adverse effects on living organisms, are extensively and increasingly used in human and veterinary medicine and are released continuously into the environment. A variety of pharmaceuticals have been detected in many environmental samples worldwide. Their occurrence has been reported in sewage-treatment-plant effluents, surface water, seawater, groundwater, soil, sediment and fish. This paper provides an overview of recent scientific research on the sources, occurrence, and fate of pharmaceuticals in water and wastewater.

Vegetable and synthetic tannins induce hormesis/toxicity in sea urchin early development and in algal growth.

Mimosa tannin and phenol-based synthetic tannin (syntan) were tested for toxicity to sea urchin (Paracentrotus lividus and Sphaerechinus granularis) early development and to marine algal growth (Dunaliella tertiolecta). Sea urchin embryogenesis was affected by vegetable tannin and syntan water extracts (VTWE and STWE) at levels >or=1mg/L. Developmental defects were significantly decreased at VTWE and STWE levels of 0.1 and 0.3mg/L when control cultures displayed suboptimal quality, i.e. <70% "viable" (normal or retarded) larvae. Fertilization success of sea urchin sperm was increased up to 0.3 mg/L STWE or VTWE, then was inhibited by increasing tannin levels (1-30 mg/L). Offspring abnormalities, following sperm exposure to VTWE or STWE, showed the same shift from hormesis to toxicity. Cell growth bioassays in D. tertiolecta exposed to VTWE or STWE (0.1-30 mg/L) showed non-linear concentration-related toxicity. Novel criteria are suggested in defining control quality that should reveal hormetic effects.

Effect of perozonation on biodegradability and toxicity of a penicillin formulation effluent.

The pretreatment of synthetic penicillin formulation effluent containing Procain Penicillin G (PPG) with the O(3)/H(2)O(2) process (applied ozone dose = 1440 mg h-1 treatment time = 60 minutes; pH 7; H(2)O(2) = 10 mM) was investigated. The effect of chemical pretreatment was assessed on the basis of acute toxicity and biodegradability with activated sludge using water flea Daphnia magna toxicity and activated sludge inhibition tests. Biological treatability studies were performed with a mixture of untreated or pretreated PPG effluent (25% on volume basis) and synthetic domestic wastewater simulating readily biodegradable organic substrate to simulate the characteristics of domestic wastewater (75% on volume basis). Pretreatment of PPG effluent the O(3)/H(2)O(2) process resulted in more than 70% chemical oxygen demand (COD) removal and a 50% decrease in the acute toxicity towards Daphnia magna. On the other hand, biodegradation of untreated PPG effluent needed prolonged acclimation periods to obtain a significant biological COD removal (= 80%). Pretreatment employing the O(3)/H(2)O(2) process not only decreased the ultimate biodegradability of PPG effluent but also increased its inhibitory effects on activated sludge treatment speculatively due to the formation of less biodegradable oxidation by-products.

The effect of pre-ozone oxidation on acute toxicity and inert soluble COD fractions of a textile finishing industry wastewater.

The present work evaluates pre-ozonation for removal of acute toxicity, color and COD as well as reduction of inert soluble COD fractions in two wastewater samples (S1 and S2) taken from a textile finishing industry, located in Istanbul (Turkey). The wastewater samples were oxidized at original pH of 8.6-8.8 under 18.5-24 mg/L of applied ozone doses. Acute toxicity was monitored using Daphnia magna. The results showed that pre-ozonation improved the biodegradability and reduced the acute toxicity. Acute toxicity in raw wastewaters was reduced by 80-90% using 129-200 mg/L transferred ozone (TrO(3)) concentrations. At this point, 86-96% of color, 33-39% of soluble COD and 57-64% of total COD were removed from wastewaters. Both color and COD parameters were found related to the acute toxicity of the wastewater. Pre-ozonation decreased the inert soluble COD fraction (S(I)) of raw wastewater while soluble product formation (S(P)) increased slightly (5-10 mg/L). However, residual COD (the sum of S(I) and S(P)) remained below discharge limit.

Toxicity of leather tanning wastewater effluents in sea urchin early development and in marine microalgae.

This study was designed to investigate the composition and the toxicity of leather tanning wastewater and conditioned sludge collected at the leather tanning wastewater treatment plant (CODISO) located in Solofra, Avellino (Southern Italy). Samples were analyzed for their conventional parameters (COD, TSS, chromium and ammonia) and for metal content. Effluent samples included raw wastewater, and samples collected following coagulation/flocculation process and biological treatment. A set of toxicity endpoints were tested using sea urchin and marine microalgal bioassays by evaluating acute embryotoxicity, developmental defects, changes in sperm fertilization success and transmissible damage from sperm to the offspring, and changes in algal growth rate. Dose-related toxicity to sea urchin embryogenesis and sperm fertilization success was exerted by effluent or sludge samples according to the following rank: conditioned sludge > coagulated effluent > or = raw influent >> effluent from biological treatment. Offspring quality was not affected by sperm exposure to any wastewater or to sludge samples. Algal growth was inhibited by raw or coagulated effluent to a similar extent and, again, the effluent from the biological treatment resulted in a decreased toxicity. The results suggest that coagulated effluent and conditioned sludge result in higher toxicity than raw influent in sea urchin embryos and sperm, whereas the biological wastewater treatment of coagulated effluent, in both sea urchins and algae, cause a substantial improvement of wastewater quality. Hence a final biological wastewater treatment should be operated to minimize any environmental damage from tannery wastewater.

Acute toxicity removal in textile finishing wastewater by Fenton's oxidation, ozone and coagulation-flocculation processes.

This study evaluates the effectiveness of Fenton's oxidation (FO) process and ozone (O3) oxidation compared with a coagulation-flocculation (CF) process to remove effluent toxicity as well as colour and COD from a textile industry wastewater. Daphnia magna was used to test acute toxicity in raw and pre-treated wastewater. The operational parameters for each process were determined on the basis of complete toxicity removal. The FO process removed COD at a higher rate (59%) than O3 (33%) while colour removal was similar (89% and 91%, respectively). The CF process removed both COD and colour at rates similar to the FO process. A colour range of 150-250 platin-cobalt (Pt-Co) unit was assessed for toxicity.

Color and COD removal from wastewater containing Reactive Black 5 using Fenton's oxidation process.

In this study, Reactive Black 5 (RB5) was removed from synthetic wastewater using Fenton's oxidation (FO) process. Experiments were conducted on the samples containing 100 and 200 mg l(-1) of RB5 to remove the dye toxicity. Seventy-five milligram per litre of RB5 caused 25% toxicity on 24-h born daphnids whereas 100 mg l(-1) of RB5 displayed 100% toxicity on Daphnia magna. The study was performed in a systematic approach searching optimum values of FeSO(4) and H(2)O(2) concentrations, pH and temperature. Optimum pH and temperature for 100 mg l(-1) of RB5 were observed as 3.0 and 40 degrees C, respectively, using 100 mg l(-1) of FeSO(4) and 400 mg l(-1) of H(2)O(2) resulted in 71% chemical oxygen demand (COD) and 99% color removal. For 200 mg l(-1) of RB5, 84% COD removal was obtained using 225 mg l(-1) of FeSO(4) and 1000 mg l(-1) of H(2)O(2) yielding 0.05 molar ratio at pH 3.0 and 40 degrees C. Color removal was also more than 99%. The optimum conditions determined in accordance with the literature data. The H(2)O(2) requirement seems to be related to initial COD of the sample. FeSO(4)/H(2)O(2) ratios found were not changed for both concentrations. The temperature affected the COD removal significantly at high degrees. Toxicity was completely removed for each concentration of RB5 at optimum removal conditions.

Removal of color and COD from a mixture of four reactive azo dyes using fenton oxidation process.

This study was designed to decolorize and to reduce COD content in a mixture of four reactive dyes, i.e., Remazol Black 5 (RB5), Remazol Red RB (RR), Remazol Yellow 84 (RY), Remazol Brilliant Blue (RB) using Fenton Oxidation Process (FOP). Optimum pH, temperature, and the doses of FeSO4 and H2O2 were determined. Experiments were conducted on the samples containing a total concentration of 100 mgL(-1) (RB+RY), 200 mg L(-1) (RB5+RR), 300 mg L(-1) (RB5+RR+RB+ RY), and 400 mg L(-1) (RR+RB+RY) dyes considering their actual application doses in dyehouses. Optimum pH was observed as 2.5 at 30 degrees C using 400 mg L(-1) FeSO4 and 800 mg L(-1) of H2O2 resulting in more than 96% COD and 99% Pt-Co unit of color removal for the mixture of RB5 and RR. The optimum conditions determined were 4.0 pH, 50 degrees C, and 500 mg L(-1) FeSO4 applying 1000 mg L(-1) H2O2 for the mixture of (RB5+RR+RB+RY). A 100 mg L(-1) solution of a mixture of RB and RY at equal amounts was oxidized using 200 mg L(-1) FeSO4 and 300 mg L(-1) H2O2 at 3.0 pH and 50 degrees C.

An OUR-based approach to determine the toxic effects of 2,4-dichlorophenoxyacetic acid in activated sludge.

This study uses the oxygen uptake rate (OUR) measurement to measure toxicity effects of 2,4-dichlorophenoxyacetic acid (2,4-D) on activated sludges fed with the wastewater from a small domestic wastewater treatment plant and peptone-based synthetic wastewater. Two 2l lab-scale batch reactors were run in parallel with the same F/M ratios (0.4 mg COD per mg VSS per day) to assess the inhibition effects of 2,4-D concentrations between 25 and 75 mg l(-1) considering at least a 100% dilution rate, as compared with a pesticide industry effluent containing 20,000-40,000 mg l(-1) COD, reaches a central treatment plant. It was noted that the OUR was decreased to 15 and 30%, respectively, when adding 75 mg l(-1) of 2,4-D to the domestic and synthetic reactors. Meanwhile, the addition of 25 plus 50 mg l(-1) of 2,4-D in sequence to the domestic wastewater reactor did not significantly affect the OUR profile. The OUR-based inhibition definition has been used in this research since the OUR methods have been frequently used and cited in the literature to study toxicity effects. However, the origin of the sludge used in the testing is also important. Synthetic wastewater may simulate the toxicity studies but with a higher response than actual systems, since the microorganisms are considerably becoming substrate-selective.