S. Meriç

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.

Degradation of diclofenac by TiO2 photocatalysis : UV absorbance kinetics and process evaluation through a set of toxicity bioassays

In the present study the degradation kinetics and mineralization of diclofenac (DCF) by the TiO(2) photocatalysis were investigated in terms of UV absorbance and COD measurements for a wide range of initial DCF concentrations (5-80mgL(-1)) and photocatalyst loadings (0.2-1.6gTiO(2)L(-1)) in a batch reactor system. A set of bioassays (Daphnia magna, Pseudokirchneriella subcapitata and Artemia salina) was performed to evaluate the potential detoxification of DCF. A pseudo-first-order kinetic model was found to fit well most of the experimental data, while at high initial DCF concentrations (40 and 80mgL(-1)) and at 1.6gTiO(2)L(-1) photocatalyst loading a second-order kinetic model was found to fit the data better. The toxicity of the treated DCF samples on D. magna and P. subcapitata varied during the oxidation, probably due to the formation of some intermediate products more toxic than DCF. Unicellular freshwater algae was found to be very sensitive to the treated samples as well as the results from D. magna test were consistent to those of algae tests. A. salina was not found to be sensitive under the investigated conditions. Finally, UV absorbance analysis were found to be an useful tool for a fast and easy to perform measurement to get preliminary information on the organic intermediates that are formed during oxidation and also on their disappearance rate.

Heterogenous photocatalytic degradation kinetics and detoxification of an urban wastewater treatment plant effluent contaminated with pharmaceuticals

Degradation kinetics and mineralization of an urban wastewater treatment plant effluent contaminated with a mixture of pharmaceutical compounds composed of amoxicillin (10 mg L(-1)), carbamazepine (5 mg L(-1)) and diclofenac (2.5 mg L(-1)) by TiO(2) photocatalysis were investigated. The photocatalytic effect was investigated using both spiked distilled water and actual wastewater solutions. The process efficiency was evaluated through UV absorbance and TOC measurements. A set of bioassays (Daphnia magna, Pseudokirchneriella subcapitata and Lepidium sativum) was performed to evaluate the potential toxicity of the oxidation intermediates. A pseudo-first order kinetic model was found to fit well the experimental data. The mineralization rate (TOC) of the wastewater contaminated with the pharmaceuticals was found to be really slow (t(1/2)=86.6 min) compared to that of the same pharmaceuticals spiked in distilled water (t(1/2)=46.5 min). The results from the toxicity tests of single pharmaceuticals, their mixture and the wastewater matrix spiked with the pharmaceuticals displayed a general accordance between the responses of the freshwater aquatic species (P. subscapitata>D. magna). In general the photocatalytic treatment did not completely reduce the toxicity under the investigated conditions (maximum catalyst loading and irradiation time 0.8 g TiO(2) L(-1) and 120 min respectively).

Ultrasonic degradation, mineralization and detoxification of diclofenac in water: Optimization of operating parameters

The 20 kHz ultrasound-induced degradation of non-steroidal, anti-inflammatory drug diclofenac (DCF) was investigated. Several operating conditions, such as power density (25-100 W/L), substrate concentration (2.5-80 mg/L), initial solution pH (3.5-11), liquid bulk temperature and the type of sparging gas (air, oxygen, argon), were tested concerning their effect on DCF degradation (as assessed measuring absorbance at 276 nm) and hydroxyl radicals generation (as assessed measuring H(2)O(2) concentration). Sample mineralization (in terms of TOC and COD removal), aerobic biodegradability (as assessed by the BOD(5)/COD ratio) and ecotoxicity to Daphnia magna and Artemia salina were followed too. DCF conversion is enhanced at increased applied power densities and liquid bulk temperatures, acidic conditions and in the presence of dissolved air or oxygen. The reaction rate increases with increasing DCF concentration in the range 2.5-5mg/L but it remains constant in the range 40-80 mg/L, indicating different kinetic regimes (i.e. first and zero order, respectively). H(2)O(2) production rates in pure water are higher than those in DCF solutions, implying that decomposition basically proceeds through hydroxyl radical reactions. Mineralization is a slow process as reaction by-products are more stable than DCF to total oxidation; nonetheless, they are also more readily biodegradable. Toxicity to D. magna increases during the early stages of the reaction and then decreases progressively upon degradation of reaction by-products; nevertheless, complete toxicity elimination cannot be achieved at the conditions in question. Neither the original nor the treated DCF samples are toxic to A. salina.

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.

Removal of Color and COD from a Mixture of Four Reactive Azo Dyes Using Fenton Oxidation Process

Abstract 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 mg L−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°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°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°C.

Developmental, cytogenetic and biochemical effects of spiked or environmentally polluted sediments in sea urchin bioassays

Sea urchin embryos and gametes have been utilised in toxicity testing for complex mixtures such as sediment samples. A number of toxicity endpoints can be evaluated by means of sea urchin bioassays, including developmental defects, changes in fertilisation success, offspring quality, and cytogenetic abnormalities. The present investigation has attempted to develop new methods focussing on a relationship between the well-established procedures based on embryological and cytogenetic endpoints, and a new approach based on measurements of redox activities in developing sea urchin larvae, by means of chemiluminescence methods and the measurement of reduced glutathione levels. The aim of this study was to evaluate the toxicity of either spiked or environmentally occurring sediment. Spiking was carried out by using some selected inorganics [Cd(II), Cu(II), Al(III) and Fe(III)] and a herbicide, pentachlorophenol (PCP). Environmental sediments were tested on samples collected in a series of sentinel sites in the Mediterranean, North Sea and Baltic Sea.

Wastewater management for Istanbul: Basis for treatment and disposal

A number of studies have so far been conducted to assess the magnitude of pollution generated by domestic and industrial sources in the Istanbul Metropolitan Area. They indicate that a management scheme for wastewater treatment and disposal should involve a total discharge of 15.4 m3 s(-1) with a potential pollution load of 330 tons BOD5 day(-1) for 1990. A scheme of this magnitude inevitably requires careful evaluation of receiving water characteristics, both from an oceanographic and a quality standpoint. In this paper significant water quality parameters related to the Black Sea-Bosphorus Strait-Marmara Sea System are reviewed and incorporated in the evaluation of treatment and disposal alternatives. In this context, the pollution exchange between the Mamara Sea and Bosphorus is quantified, pollutant contents of the Mamara Sea and discharges from the Istanbul Metropolitan Area are compared, and a number of scenarios are evaluated to define the optimum treatment and disposal strategy.

MICROBIAL AND COD REMOVAL IN A MUNICIPAL WASTEWATER TREATMENT PLANT USING COAGULATION FLOCCULATION PROCESS

ABSTRACT This study was designed to improve the removal efficiency of COD, SS, and microorganism at the S. Giovanni a Teduccio municipal wastewater treatment plant, Naples, Italy. The plant consists of screen, sand grinder, oil removal, coagulation, flocculation and sedimentation units, hypochlorite disinfection, mechanical dewatering, and thermal sludge conditioning. A series of Jar-test was conducted on twelve samples taken after screen using FeSO4 alone or together with Ca(OH)2 at 100 rpm rapid mixing for 1 min, 30 rpm for slow mixing for 20 min and 30 min for settling. 150 mg L−1 and 450 mg/L doses of FeSO4 were used at a pH interval in between 6 and 9. The removals of COD, TSS, Escherichia coli and total coliforms were measured ranging from 40 to 70%, 70 to 90%, 96 to 99% and 97 to 99%, respectively when FeSO4 was used alone at 150 mg L−1 and 450 mg L−1 doses and at pH 6, 7 and 8. Wastewater discharge standards could be safely obtained at 150 mg L−1 dose of FeSO4 with the use of 220 mg L−1 Ca(OH)2 at pH 8 in terms of COD and E. coli removals resulted in 65% and 98%, respectively, with less sludge production to be disposed. Additionally, none of influent and supernatant samples tested in this study was found to be acute toxic on 24 h-born Daphnia magna at 50% dilution.

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 O3/H2O2 process (applied ozone dose = 1440 mg h−1 treatment time = 60 minutes; pH 7; H2O2 = 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 O3/H2O2 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 O3/H2O2 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.