Waste Water Treatment and Reutilization 2011 Part 3 ppt

Removal of Endocrine Disruptors in Waste Waters by Means of Bioreactors 43 From the industrial point of view, the results discussed above indicate a substantial reduction in the processing times to bioremediate water polluted by DMP and thus a reduction in the process’s costs. In fact, it is possible to correlate the parameters α or P.A.I., which are functions of ∆T, with the reduction in the bioremediation time, τ r , defined as () - % x 100 iso non iso r iso ττ τ τ − = (13) where τ iso and τ non-iso are the time required to obtain the same percentage of DMP biodegradation under isothermal and non-isothermal conditions, respectively. To correlate τ r with the applied ∆T* it is necessary to calculate the time required to obtain the same amount of DMP removal under isothermal and non-isothermal conditions. This calculation can be done graphically or analytically. Fig. 10. DMP in function of reaction time. z: ∆T=0°C; Δ: ∆T=10°C; {: ∆T=20°C; : ∆T=30°C. As one example of the graphical calculation let us see Figure 10, where we has been reported as a function of the time of enzyme treatment, the DMP decrease in the case of T average =25°C, with ΔT=0 or 10 or 20 or 30°C. The initial DMP concentration was 5 mM. To obtain the same biodegradation of DMP, for example a 50% reduction, 161 minutes are needed for the isothermal condition, while 145 or 134 or 125 minutes are required for ΔT=10°C, ΔT=20°C, ΔT=30°C, respectively. It follows that a value of τ r =9.9% is obtained with a ΔT=10°C, a τ r =16.8% with a ΔT=20°C, and a τ r =25% with a ΔT=30°C. The τ r values increase with an increase in the applied ΔT and therefore with the P.A.I. The analytical approach is based on the consideration that the same DMP degradation is obtained when RR C,ΔT=0 . τ iso = RR C,ΔT≠0 . τ non-iso ,, where RR stands for the reaction rate. By recalling that C, T0 iso C, T0 non-iso RR RR 1 T 100 α ττ Δ= Δ= ⎛⎞ =+Δ ⎜⎟ ⎝⎠ (14) after a series of mathematical steps one obtains ** ** (%) 100 100 100 100 100 . . . 100 r TTPAI TPAI T αα τ α α ⎛⎞ ΔΔ ⎛⎞ ⎛ ⎞ == = ⎜⎟ ⎜⎟ ⎜ ⎟ ⎜⎟ Δ+ + Δ+ ⎝⎠ ⎝ ⎠ ⎝⎠ (15) Waste Water - Treatment and Reutilization 44 In Figure 11a, the τ r values obtained at different DMP concentrations with ΔT=30°C have been reported as a function of the P.A.I. calculated for each DMP concentration. As expected, the reduction in bioremediation time is an increasing function of the percentage increase in the enzyme activity (P.A.I.) and, consequently, in the temperature difference applied across the membrane. Highlighted in black is the case for a DMP concentration equal to 5 mM, for which the P.A.I. is 33.4% and the τ r is 25%. b) 0 5 10 15 [DMP ] (mM ) 0 20 40 60 80 100 τ r ( % ) 0 20 40 60 80 100 τ r ( % ) 0 20 40 60 80 100 P.A.I. (%) a) Fig. 11. (a): Percentage reduction of the productions time (τ r ) in function of Percentage Activity Increase. (b): τ r in function of DMP concentration. Because the P.A.I. is related to the substrate concentration, we have reported the reduction in biodegradation time as a function of the DMP concentration in Figure 11b. Again, highlighted in black is the result relative to the DMP concentration of 5 mM. As is evident from Figure 11b, the reduction in the biodegradation time decreases with the increase in the DMP concentration. Also, this result is interesting for practical applications, because the concentrations used by us are higher than those actually found in polluted water, owing to DMP’s small solubility in water. From the above results, it follows that the decrease in DMP concentration is a linear function of the applied temperature difference and is inversely proportional to the initial DMP concentration. To quantify this observation, in Table 4 we have reported the percentage decreases of DMP concentration after 180 minutes of enzyme treatment. [DMP] T av (°C) ∆T (°C) 1 mM 3 mM 5 mM 8 mM 0 68.5 % 63.0 % 58.1 % 43.4 % 10 84 .0 % 72.5 % 66.1 % 47.7 % 20 100.0 % 82.7 % 72.9 % 51.9 % 25 30 100.0 % 89.5 % 79.3 % 55.1 % Table 4. Percentage decreases of DMP concentration after 180 minutes of enzyme treatment. 7. Conclusions The obtained results have shown that the laccase from Trametes versicolor and the tyrosinase from mushrooms immobilized on PAN beads filling a fluidized bed bioreactor are able to Removal of Endocrine Disruptors in Waste Waters by Means of Bioreactors 45 oxidize different bisphenols. In particular, the BPF is the substrate towards which the immobilized enzymes have the highest bioremediation power. Moreover the higher removal efficiencies (≈100%) for all bisphenols were obtained with immobilized laccase. The immobilized tyrosinase, under the same experimental conditions, showed smaller removal efficiency (~90%), notwithstanding the specific activity of this enzyme results to be 1500U/mg, about 75 time that of laccase. Coming to the experiments carried out in planar membrane bioreactors working under non- isothermal conditions, the results have shown the possibility of using the enzyme lipase from Candida rugosa in the pathway for the biodegradation of phthalates to bioremediate water polluted by these compounds. The use of non-isothermal bioreactors proved the utility of this technology in solving some of the pollution problems affecting human life and wildlife. Moreover, our studies may increase the limited knowledge regarding the direct exploitation of purified enzymes in the hydrolysis of phthalates, since the literature exhibits very few papers in this field. 8. Perspectives Our results encourage new studies in order to bioremediate waters polluted by EDCs. By considering that in real samples EDCs are present in mixture, it will be interesting for the future to coimmobilize different enzymes able to hydrolyze different pollutants. But a more intriguing observation can be advanced by considering the meaning of the word “cleaning up”. From the analytic point of view “cleaning up” means to “reduce or eliminate” the pollutant concentration. From the biological point of view, indeed, and particularly in the case of EDCs, besides “the reduction or elimination” of the pollutant concentration, “cleaning up” means the removal of the endocrine effects observed before the enzyme treatment. So, tests on cell line and on living organisms are request to assess the toxicity or the endocrine power of the reaction products. If these tests will result negative, only in this case we can speak of occurred “cleaning up”. 9. 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The anaerobic treatment is defined as the biological separation of organic wastes in anaerobic conditions and also the production of their last products, such as CH 4 , CO 2 , NH 3 , and H 2 S (biogas). The processes, employed by anaerobic bacteria, have been widely used in treatment of municipal wastewaters and varying types of industrial wastewaters for removal of organic material in the wastewaters and also produce biogas as energy from the wastewaters. Treatment capacity of an anaerobic digestion system is primarily determined by the amount of active microorganism population retained within the system dependent on wastewater composition, system configuration and operation of anaerobic reactor (Zainol et al., 2009). 2. Important Textiles and apparel sector, one of the important industries in the world, is a vital contributor to Turkey's economy, accounting for approximately 10 percent of the country's gross domestic product. It is the largest industry in the country, constituting approximately 15 percent of manufacturing and about one-third of manufactured exports. Nowadays, the country produces the eighth-largest volume of man-made fibers in the world, at 1.2 million tons per year (Pelot, n.d.). Therefore, textile industries are vitally distributed in the country. The variety of raw materials, chemicals, processes and also technological variations applied to the processes cause complex and dynamic structure of environmental impact from the textile industry (Sapci & Ustun, 2003). The textile industries as pretreatment (desizing - scouring - bleaching) and dyeing processes generate large quantity of wastewater containing unreacted dyes, suspended solids, dissolved solids, and biodegradable and non- biodegradable other auxiliary chemicals (Raju et al., 2008, Somasiri et al., 2008, Georgiou et al., 2005, Isik & Sponza 2004). For example, polyester is a material produced on a large scale Waste Water - Treatment and Reutilization 50 as a component of textile fiber, which results in a great deal of discharge wastewater with various additives and detergents, including wetting agents, softening agents, antioxidant, surfactant, detergent, antiseptic and dyes (Yang, 2009). Cliona et al. (1999) reported that the dyes can be classified on their chemical structure (azo, anthraquinone, azine, xanthene, nitro, phthalocyanine, etc.) or application methods used in the dyeing process (acid, basic, direct, reactive, etc) (Somasiri et al., 2008). Therefore, these industries have also shown a significant increase in the use of synthetic complex organic dyes as coloring material. The discharge of these textiles is viewed to have negative effect on the environment in this area, also damaging the quality of water sources and may be toxic to treatment processes, to food chain organisms and to aquatic life (Talarposhti et al., 2001). Therefore, it is of paramount importance to know its exact nature, in order to implement an appropriate treatment process (Marmagne & Coste, 1999). For the foregoing reasons, textile industries wastewater was selected for the research. On the other hand, the country has around 1.9 million employees in the textile and apparel sector (Pelot, n.d.). Therefore, wastewater of these industries has generally been a combination of textile and municipal wastewater. If the municipal wastewater mixes with the other kind of wastewater, it has lost its domestic property, and is considered to be process wastewater. Biological treatment may be a good alternative as the operational costs are relatively low when compared to most of the physical/chemical technologies. Although recent studies of anaerobic treatment of textile wastewater using several high-rate up-flow anaerobic sludge blanket reactors were conducted, however studies about anaerobic treatment of mixture wastewater (both textile and municipal wastewater) are deficient. For the foregoing reasons, between textile industries wastewater and municipal wastewater were applied for the research. The aim of this work was to study the treatment of textile wastewater using an up-flow anaerobic sludge blanket (UASB). Textile wastewater was selected for the research due to its total volume (53.5% of all types of industry in Turkey). In this study, firstly, treatability of textile polyester wastewater diluted with a municipal one is examined in an UASB system according to organic loading rate (OLR), hydraulic retention time (HRT), as well as important anaerobic operating parameters. Three reactors were operated at mesophilic conditions (37±0.5 °C) in a temperature-controlled water-bath with hydraulic retention times (HRTs) of 5 days, and with organic loading rates (OLR) between 0.314(±0.03) – 0.567(±0.05) kg COD/m 3 /day. Three different dilution ratios (45%, 30% and 15%) of municipal with real polyester textile wastewater are employed. Secondly, the effects of glucose and lactose selected as a co-substrate, with constant HRT values of 5 days, on the systems with same dilution ratios for each reactor (30%) were examined. All these results evaluated in the manuscript. Thirdly, to show a difference of anaerobic treatability between polyester wastewater diluted with municipal wastewater and cotton textile wastewater diluted with municipal wastewater, all these results compared with previous study (Zengin & Aydinol, 2007). The previous study about real cotton textile wastewater treatment were run two hydraulic retention times (HRTs) of 4.5 and 9.0 days, and with organic loading rates (OLR) between 0.087(±0.016) – 0.517(±0.090) kg COD/m 3 /day. Three different dilution ratios (15%, 30% and 40%) of municipal with textile wastewater were employed at same mesophilic conditions. Fourthly, regarding mixed wastewater, co-substrate effect on anaerobic treatment evaluated according to COD removal efficiency. For this reason, assessment of anaerobic treatment results from previous experiments which were used glucose (as co- substrate) with varied dilution ratios (60%, 40%, 45%, 30%, and 15%) of municipal with Evaluation of Anaerobic Treatability of Between Cotton and Polyester Textile Industry Wastewater 51 cotton textile wastewater experiments and these trials which were used same co-substrate with different dilution ratios (45%, 30% and 15%) of municipal with real polyester textile wastewater were examined. The results showed that the municipal wastewater rate in both the polyester wastewater and the cotton wastewater did not have a substantial change in COD removal efficiency. Textile polyester wastewater diluted with different ratio of municipal one was not treated in UASB as a satisfied for COD removal efficiency even though values of alkalinity, SS and pH are founded optimum range for successful operation of the digester. In addition, even if when either glucose or lactose as a co-substrate was added mixed wastewater; it was not seen positive effect for anaerobic treatment of polyester wastewater. However, addition of co- substrate (glucose) in cotton wastewaters had a positive effect on the COD removal efficiency. Therefore, COD removal efficiency of textile wastewater on anaerobic digestion change especially depends on textile wastewater types. Before the anaerobic treatment of polyester wastewater, it should be treated via advance technology. 3. Information 3.1 Sampling In this study, original wastewater samples were obtained from the knit fabric wastewater and polyester process wastewater of two different industries located in Istanbul, Turkey. First industry, knit fabric industry, dyed of fiber, wool yarn and fabric (before knit process) or texture (after the unit). This industry wastewater was used during the start-up period of anaerobic treatment in the study. Second industry uses only polyester fabrics which are dyed using dispersive dyes. Used cotton textile wastewater for comparing of anaerobic treatment results in the study was taken from another industry in Istanbul, which detail information was given previous study (Zengin & Aydinol, 2007). In addition, municipal wastewater used for dilution was supplied from a municipal wastewater plant in Istanbul. All samples were delivered to the laboratory cooled and kept 4 ° C during the experimental study. 3.2 Experimental set-up Three reactors, made of serum bottles similar to studies cited in literature (Tang et al., 1999, Sacks & Buckley, 1999, Cordina et al., 1998, Fang & Chan, 1997, Madsen & Rasmussen 1996, Soto et al., 1993, Guiot et al, 1986) were used, each having a volume of 1.2 L and operated for 80 days at mesophilic conditions (37±0.5 °C) in a temperature-controlled water- bath (Ben- Marie device) with two hydraulic retention times (HRTs) of 4.5 and 9.0 days (Fig 1). The upper side of the reactors (14% of reactor volume) had a slope similar to a gas collection funnel. The biogas collected here was measured by the method of volume displacement. Prior to experiments, 3 UASB reactors were inoculated with granular biomass (25% of the working volume) obtained from Tekel Brewery Inc. (Istanbul, Turkey) and N 2 gas passed through them. The reactors then were filled to their respective volumes with textile wastewater (61% of the total volume). After the start-up period, the real textile wastewater obtained from effluent of textile houses in Istanbul, Turkey fed to the reactors with domestic wastewater. The treatment process was monitored and components of wastewater samples were analyzed in the Environmental Engineering Laboratory at Yildiz Technical University (YTU), Istanbul, Turkey. A detailed schematic diagram of the experimental set-up is shown in Fig. 1. Waste Water - Treatment and Reutilization 52 C l i f t o n O n O f f 2 W a t s o n M a r l o w 1 R1 R2 R3 12 3 4 9 5 6 7 8 10 11 13 Notations with explanations (1) Feeding tank (2) Time controlled peristaltic pump (3) Temperature controlled water bath (4) Adjustable heater with thermostat (5) Suction pipe (6) Influent pipe (7) Effluent pipe (8) Gas collecting pipe (9) Gas bag (10) Gas sampling valve (11) Gas collecting tube (12) Measuring tube (13) Power cord (R1) Reactor-1 (R2) Reactor-2 (R3) Reactor-3 Fig. 1. Detailed schematic of the experimental set-up 3.3 Analytical methods The temperature, pH, biogas volume (ml) and COD removal efficiency (%) were measured daily. Alkalinity (mg/L as CaCO 3 ), TSS (Total Suspended Solids) (mg/L), and VFA (Volatile Fatty Acids) were measured three times a week according to Standard Methods of APHA- AWWA (1995) (Table 1). During the study, the operational temperatures of the reactors were monitored with a digital thermometer, and pH was measured by a Jenway 3040 Ion Analyzer. The other parameters were determined by the procedures described in Method Numbers 5220-B (Open Reflux Method for COD), 2320-B (Titration Method for Alkalinity), 2540-D (Total Suspended Solids Dried at 103-105 °C) and 5560-C (Distillation Method for VFA) respectively. Concentration of heavy metals (Table 1) were analyzed by the procedure described in Method Number 3111-B (Direct Air Acetylene Flame Method) with an ATI Unicam 929AA-Spectrometer. Hydraulic retention time (HRT) is a measure of the amount of time the digester liquid remains in the digester. Organic loading rate (OLR) is a measure of the biological conversion capacity of the anaerobic treatment system. COD removal efficiency (COD RE ) of UASB reactors being output parameter was considered as a measure of treatment performance. COD RE value is defined as follows: COD RE (%) = (COD i – COD e ) / COD i * 100 (1) where COD i is the influent COD concentration and COD e is the effluent COD concentration. Six anaerobic reactors having a total volume of 200 ml were also operated to determine COD fractions of wastewater samples. These reactors were conducted for about 1800 hours at mesophilic conditions (37±0.5 °C), maintained by an adjustable aquarium heater with thermostat (Otto Aquarium Company, Taiwan). Each of them was seeded with 30 mg/L as Mixed Liquor Volatile Suspended Solids (MLVSS) of acclimated granular sludge and homogenized with 100 ml of textile and municipal wastewater. Filtrates of samples obtained from vacuum filtration by means of glass microfibre filters having a pore size of 0.45 µm (Whatman glass microfibre filter) were defined as "soluble fractions". Filter wastewaters and raw wastewaters were fed in the different COD fraction reactors. [...]... polyester wastewater and municipal wastewater with co-substrate (2nd system) and cotton last process wastewater and th th municipal wastewater with co-substrate (6 and 7 system) nd system (mixed wastewater charges including 45, Results of anaerobic treatability of both 2 30 and 15% of municipal wastewater with real polyester textile wastewater) and 6th system (60, 45 and 30 % of municipal wastewater with... 7.7±-0.2 7 .35 ±0.8 7 .35 ±0.8 7.1±0.6 7 .35 ±0.8 7.05±0.6 7.05±0.4 pH 635 ±15 610±110 605±5 510±10 475±25 525±75 31 3 30 32 3±54 281±124 570±40 585±15 565±25 575±50 565±65 565±85 475±40 467±65 465±87 VFA (mg/L) 99± 31 67±21 34 ±16 81±12 188±86 202±115 1475 ±25 131 ±54 1425±25 137 5±25 1650± 130 101±19 1600±200 80 35 67± 43 69±50 75 30 75 30 53 14 101 38 75±29 107±55 68±22 195±15 30 ±12 72±22 67 33 70±20 77±22 67 33 - -... efficiency 56 Waste Water - Treatment and Reutilization 45% diluted wastewater 30 % diluted wastewater 15% diluted wastewater 100 COD RE (%) 80 60 40 20 0 0 50 100 150 200 250 30 0 35 0 400 450 30 0 35 0 400 450 30 0 35 0 400 450 30 0 35 0 400 450 Time (hours) 8 pH 7,5 7 6,5 6 0 50 100 150 200 250 Time (hours) 1600 Alkalinity(mg/mL as CaCO 3 ) 1400 1200 1000 800 600 400 200 0 0 50 100 150 200 250 Time (hours) 30 0 Biogas... OLR (kgCOD/m3/d) 9 9 9 4.5 4.5 4.5 5 5 5 9 9 0 .31 1±0.620 0 .31 3±0.051 0 .31 3±0.052 0.517±0.090 0.494±0.077 0.468±0.082 0.408±0.14 0 .31 4±0. 03 0 .31 9±0.05 0.087±0.016 0.089±0.007 0.088±0.0 03 0.224±0.06 4.5 9 0.175±0.02 4.5 0.175±0.02 5 4.5 0.567±0.005 5 5 HRT (days) 69 75 76 32 28 36 ~30 ~35 ~45 46 50 53 40 46 53 5 5 5 CODRE (%) 7.0±0.2 7.0±0.1 6.7±0.4 7 .3 0 .3 7.2±0 .3 7.2±0.2 7 .3 0.1 7.2±0.1 7 .3 0.1 7.7±0.2... 40, 30 , and 15% of municipal wastewater in the 4th system showed similar COD removal efficiencies of 53, 46 and 40%, respectively As a result, it was observed that the municipal wastewater rate in both the polyester wastewater and the cotton wastewater Evaluation of Anaerobic Treatability of Between Cotton and Polyester Textile Industry Wastewater 30 % diluted wastewater with glucose 59 30 % diluted wastewater... textile wastewaters and particulate inert microbial products are measured almost same ratio, 15% for cotton wastewater and 13% for polyester wastewater Because the inert part is not biodegradable, this COD fraction is measured as the same value in effluent water Total (particular and soluble) inert COD and total (particular and soluble) inert microbial product are measured as 25% for the cotton and 33 %... polyester wastewater Therefore, 75% of COD in cotton wastewater and 66% of COD in the polyester wastewater are biodegradable in the process The fraction of total COD in municipal wastewater was obtained to be 35 % Total particulate COD for the municipal wastewater was found to be 65% 58 Waste Water - Treatment and Reutilization COD Fractions CT ST1 SI1+SP SS1+SH1 XT1 XH+XP XH1+XS1 Polyester process wastewater... including 30 % of municipal wastewater with two different co- substrates (glucose and lactose) 60 Waste Water - Treatment and Reutilization did not have a substantial change in COD removal efficiency On the other hand, when the ratio of municipal wastewater in 4th system was increased, COD removal efficiency slightly increased (COD of effluent wastewater 630 - 635 mg/L) for the cotton wastewater treatment. .. Fig 3 Mixed wastewater charges including 45, 30 and 15% of municipal wastewater with co- substrate (glucose) Evaluation of Anaerobic Treatability of Between Cotton and Polyester Textile Industry Wastewater 57 4.4 Treatment of polyester textile wastewater with municipal wastewater and two rd different co-substrates (HRT 5 days) (3 system) Previous chapter indicated that municipal mixture ratio and added... 1757 204 16 21 34 1200 230 1750 30 0 2 175 47 . 0 .31 9±0.05 ~45 7 .3 0.1 281±124 1187±160 30 ±12 107±55 Polyester 30 Glucose 5 0 .31 4±0. 03 ~35 7.2±0.1 32 3±54 11 13 105 34 ±16 75±29 2 Polyester 15 Glucose 5 0.408±0.14 ~30 7 .3 0.1 31 3 30 130 2±99. municipal wastewater was obtained to be 35 %. Total particulate COD for the municipal wastewater was found to be 65%. Waste Water - Treatment and Reutilization 58 Polyester process wastewater. 0.517±0.090 32 7 .3 0 .3 510±10 1650± 130 81±12 75 30 Cotton 40 Glucose 9 0 .31 3±0.052 76 6.7±0.4 605±5 137 5±25 131 ±54 69±50 Cotton 30 Glucose 9 0 .31 3±0.051 75 7.0±0.1 610±110 1425±25 188±86 67± 43 7