Environ Monit Assess (2017) 189:438 DOI 10.1007/s10661-017-6128-7
Removal of micropollutants from Sakarya River water by ozone and membrane processes Fatma Büşra Yaman & Mehmet Çakmakcı & Ebubekir Yüksel & İsmail Özen & Erhan Gengeç
Received: 22 April 2016 / Accepted: 18 July 2017 # Springer International Publishing AG 2017
Abstract The removal of some pollutants in the Sakarya River was investigated in this study. Sakarya River located in Turkey flows from the northeast of Afyonkarahisar City to the Black Sea. Nineteen different micropollutants including trihalomethanes (THMs), haloacetic acids (HAAs), endocrine disrupting compound (EDC) and pharmaceuticals personal care product (PPCP) groups, and water quality parameters such as dissolved organic carbon (DOC), ultraviolet absorbance at 254 nm wavelength (UV254), hardness, and conductivity values were examined. To remove the micropollutants and improve the water quality, the F. B. Yaman (*) : M. Çakmakcı Department of Environmental Engineering, Yildiz Technical University, Istanbul, Turkey e-mail:
[email protected] M. Çakmakcı e-mail:
[email protected] E. Yüksel : İ. Özen Department of Environmental Engineering, Gebze Technical University, Istanbul, Turkey E. Yüksel e-mail:
[email protected]
treatment was performed with ozone, microfiltration (MF), and ultra-filtration (UF) membranes. The highest treatment efficiency was obtained with 1 mg/L ozone dosage and UP005 UF membrane. The trihalomethan formation potential (THMFP) and haloacetic acid formation potential (HAAFP) decreased with ozone + membrane at a concentration of 79 and 75%, respectively. After the treatment with ozone + membrane, the concentration of the micropollutants in the EDC and PPCP group remained below the detection limit. It was found that by using only membrane and only ozone, the maximum DOC removal efficiency achieved was 46 and 18%, respectively; and with ozone + membrane, this efficiency increased up to 82%. The results from the High-Pressure Size Exclusion Chromatography (HPSEC) analyses pointed that the substances with high molecular weight were converted into substances with low molecular weight after the treatment. The Fourier Transform Infrared (FTIR) analysis results showed that the aromatic and aliphatic functional groups in water changed after the treatment with ozone and that the peak values decreased more after the ozone + membrane treatment. Keywords Disinfection by-products . Endocrine disrupting compounds . Pharmaceuticals personal care products . Membrane . Ozone
İ. Özen e-mail:
[email protected] E. Gengeç Department of Environmental Engineering, Kocaeli University, Kocaeli, Turkey e-mail:
[email protected]
Introduction Surface and groundwaters are used to supply drinking water. Even if drinking water is of high quality,
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disinfection should be performed before distribution to pipes to ensure that there are no pathogens in water. Disinfection is usually applied to improve the quality of water by removing pathogens. Since the early twentieth century (Yang et al. 2010; Serrano et al. 2015), chlorine, a disinfectant for water treatment, which is extremely powerful, practical, and cost-effective, has been most widely used (Pardakhti et al. 2011; Kumari and Gupta 2015; Niu et al. 2015). However, natural organic matter (NOM) presents in drinking water sources is a major problematic issue for disinfection, because it produces disinfection byproducts (DBPs) during chlorination (Ye et al. 2009; Lamsal et al. 2012). Trihalomethanes (THMs) and haloacetic acids (HAAs) are the two DBPs found in chlorinated waters all over the world (Khan et al. 2009; Zhang et al. 2011; Aydin et al. 2012). DBPs can potentially cause long-term adverse health effects. They are potentially carcinogenetic to humans (Tubić et al. 2013; Reguero et al. 2013; Huang et al. 2015). Because of the potential health risks of DBPs, many countries like the UK, the USA, Turkey, Japan, and some water agencies, i.e., USEPA (1990) and WHO (2011) added these compounds in their drinking water quality guidelines” (Zhang et al. 2011; Reguero et al. 2013; Kumari and Gupta 2015). Drinking water sources can be polluted with a variety of contaminants. These pollutants are classified as developing micropollutants, which is a major problem in terms of environmental pollution and environmental health, because the spread of these pollutants to the environment is usually at a very low concentration (Daneshvar et al. 2010; Rivera-Utrilla et al. 2013; Jiang 2013; Jagoda et al. 2015; You et al. 2015). Pharmaceuticals personal care products (PPCPs), endocrine disrupting compounds (EDCs), and pesticides are groups of organic micropollutants routinely detected in surface and even in drinking waters (Broseus et al. 2009). By considering that even low concentrations are very influential, most micropollutants like caffeine, phtalic anhydride (PA), tris(2-chloroethyl) phosphate (TCEP), carbamazepine, naproxen, and tris(2-butoxyethyl) phosphate (TBEP), in addition to DBPs, are analyzed. Caffeine is a stimulant and is one of the mostconsumed EDCs due to its high-level consumption in daily life. Caffeine is considered as a wastewater indicator and has been reported in surface waters at concentrations in a range of 291–526 ng/L. It is also reported in the literature among the drugs of abuse (Boleda et al. 2011).
Environ Monit Assess (2017) 189:438
PA is an organic compound. It is the anhydrite of phthalic acid. It has the quality of being the first dicarboxyl acid anhydride used for commercial purposes. Phthalic anhydride, which is a colorless solid substance, is an important chemical and is used especially as a plasticizer (Akbari and Alavi 2015). Naproxen is a non-steroidal anti-inflammatory agent and is used both in medicine and in veterinary at a high concentration and is sold without recipes. Sixty of it is eliminated from the body without being metabolized and is relatively stable in the environment (Boleda et al. 2011; Grenni et al. 2013; Kosjek et al. 2015). In the study conducted by Boleda et al., naproxen was found to be between 99 and 152 ng/L. The average naproxen concentration in Mero River in Spain was found as 109 ng/L (Rodil et al. 2012). Carbamazepine is an anti-epileptic drug that works by decreasing the neural stimuli that cause seizures and pain. It is resistant to biodegradation and is mixed in the environment with domestic and medical wastewaters. It can also be released to the surface water resources from the wastewater treatment facilities due to inadequate treatment (Rodil et al. 2012). In a study conducted in 23 European countries, it was reported that there was 2–400 ng/L carbamazepine pollutant in underground water (Sui et al. 2015). TCEP is used as fluidity stabilizer in the synthesis of polymers like fire extinguishers, plastic raw material, and polyurethane polyester polyacrylate. TCEP is a carcinogenic and toxic substance and is frequently observed in wastewater discharges and in resources used for drinking water treatment. Since it is not effective to remove TCEP in wastewater and water treatment plants with conventional methods, new methods are needed. TCEP has high mobility in water due to its high polarity. For this reason, TCEP and similar substances may leave wastewater and water treatment plants without important removal (Akbari and Alavi 2015). Yoon et al. (2007) reported that TCEP pollutant was observed in the exit of the wastewater treatment plant at a concentration of 557 ng/L and in drinking water at a concentration of 99 ng/L. In a study conducted in Aire River in England, the TCEP concentration was measured at a wide range of 181–4821 ng/L (Cristale et al. 2013). TBEP is used as a fire extinguisher, floor polisher, and the raw material of rubber and plastic. This chemical may be decomposed biologically, and exists especially in bottom sediment of the surface water at a high
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concentration. This chemical, which half-life is 50 days, may mix with the sea water as well (Li et al. 2014). The annual production amount is estimated at 5000–6000 t. It is a viscose, colorless, and slightly yellowish liquid. It dissolves well in water. TBEP may be assessed as a biodegradable substance. The measurements made in wastewater treatment plants and semi-continuous sediment laboratory tests revealed that more than 80% of the TBEP is degraded. It was determined that the TBEP may degrade completely in river and coastal waters. Studies were conducted to examine the TBEP accumulation in fish used as raw material in polish production, and it was reported that this pollutant is not subject to bio-accumulation because of its water solubility level being high. Esteban et al. (2014) conducted a study and measured the TBEP concentration in North Antarctic Peninsula wastewater discharge as ranging between 9040 and 43,000 ng/L. In a study conducted in Germany in nine different surface water sources, it was reported that the TBEP and TCEP concentrations were 8–10 ng/ L and 85–126 ng/L, respectively (Regnery and Püttmann 2010). Thus, the removal of these pollutants is a vital issue for surface and groundwaters. Treatment options have been suggested for the removal of these trace organic contaminants. Recent studies have indicated that conventional drinking water treatment processes (coagulation/flocculation, filtration, chlorination) are ineffective in completely removing micropollutants (Broseus et al. 2009; Rivera-Utrilla et al. 2013; Jiang 2013; Reguero et al. 2013; Vaquero et al. 2014; Simazaki et al. 2015). The tightening of water quality regulations and the increased attention on micropollutants are calling for alternative treatment technologies to improve the treatment process (Ates et al. 2009; Reguero et al. 2013). To improve the performance of conventional treatment, advanced treatment methods have been applied (Stoquart et al. 2012; Doederer et al. 2014). Membrane technologies can be used due to their high treatment efficiency for the removal of salts, NOMs, metals, EDCs, PPCPs, and DBPs (Khan et al. 2009; Doederer et al. 2014; Vaquero et al. 2014; Sutherland et al. 2015). Vaquero et al. (2014) reported that 100% DOC, 15–97% pharmaceuticals, and 57% THM were removed with 200 Da NF membranes. Lowe and Hossain (2008) conducted a study to remove humic acid, which is one of the most important organic matters in nature, with 3, 5, and 10 kDa UF membranes, and determined that the DOC and UV254 removal efficiency in each three
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membranes was around 90%. Yang et al. (2010) reported 84.3% trihalomethan formation potential (THMFP), 94% UV254, and 97.5% haloacetic acid formation potential (HAAFP) removal efficiency with the UF (10,000 Da) and NF membrane combination. Uyak et al. (2008) conducted a study and reported that chloroform was removed up to 90–95%, bromochloromethane at 85–95%, and dibromochloromethane at 80–88% with NF200 and DS5 membranes under 10 bar pressure. In another study, dissolved organic substances with high molecular weight (DOMs) were removed at a high concentration with NF and UF membranes, and no good results were observed for the fraction with lower molecular weight (
