ࡱ> .defghijklmnopqrstuvwxyz{|}~q` bjbjqPqP k::}0>>>>$bXbXbXPXFYs2ZZZZZ/[Bq[[mrorororororor$th$wLr`+[/[``r>>ZZDsfff`>l ZZmrf`mrffVn@,YoZY @='bXbn qlZs0soTpwcpwYoYopwmo[,\f]K^[[[rrej[[[s````$)BDB>>>>>>  21th-24 th September 2008, Split, Croatia WASTE WATER PURIFYING USING WETLAND SYSTEM Parac-Osterman ., uraaevi V., Sutlovi A. University of Zagreb, Faculty of Textile Technology, Zagreb, Croatia E-mail: djparac@ttf.hr Abstract: Legislation regarding outlet wastewaters is becoming more severe and restrictive, demanding purifying processes to become more efficient, but also more expensive every day, making room for non-conventional purifying methods such as constructed wetland (CW). The system itself imitates autopurification processes which occur in nature. CW is especial suitable for waste water burdened by heterogeneous pollutants. In this paper CW was optimized within laboratory investigations and then used as an only method employed in order to purify dye-house wastewater. Optimized combination of purifying media along with Phragmites Australis achieved reduction of measured biological parameters (COD, BOD5, TOC, AOX, el. conductivity, pH, NH4+, NO3-, NO2-, total P and the amount of Cl- ions). Key words: dye-house waste water, purifying, constructed wetland, water quality 1. INTRODUCTION Constructed wetlands (CW) or man-made wetlands imitate water purifying processes that occur in nature, thus outputing highly purified water. CW combines several biological elements which all contribute sinergically to water purification. Elements that define CW are hydrology, type of soil and of course plant life. Such a complex system often attracts wild life which makes CW a living, breathing ecosystem (Fig.1) (Brown D. S., 1994; Parac-Osterman ., uraaevi V., 2005).  Figure 1. Purifying through aquaculture CWs have many advantages such as low construction and operation costs, simple installation and maintenance. CWs are being used for both small and large applications. Variations of this technology are in use to deal with single-family residences to highway runoff, landfill sites, food processing industries as well as graphic industry. On the basis of treatment efficiency, it is evident that the CW is ecologically acceptable small waste water treatment technology (Parac-Osterman . et. al. 2006 and 2007). The idea of wastewater treatment in the lagoons with floating plants and later in the CW was born in the second half of the eighties. The experiences with floating plants showed that the CWs are more suitable than lagoons because of many reasons (cold winters, potential odors and insects, large areas needed) (Braux A., 2005; Griessler-Bulc T. et al., 2005). Biological treatment presented in this paper was investigated within scientific projects: 1. Application of Fuzzy Logic in Dyeing Processes and Colour Management, Ministry of Science, Education and Sports of the Republic of Croatia; and 2. International project EUREKA: Textilwet. 2. EXPERIMENTAL 2.1. Problem statement Constructed wetlands (CW) or man-made wetlands imitate water purifying processes that occur in nature, thus outputing highly purified water. CW combines several bilogical elements which all contribute sinergically to water purification. Elements that define CW are hydrology, type of soil and of course plant life. Such a complex system often attracts wild life which makes CW a living, breathing ecosystem. This paper revises efficiency of aforesaid purifying system especially emphasizing broad spectrum of analytical methods used. Parameters measured and used for the evaluation of the waste water quality before and after the purifying process were COD, BOD5, TOC, AOX, el. conductivity, pH, NH4+, NO3-, NO2-, total P, SAC and the amount of Cl- ions. The first step in water and energy management program is preparation of facility process flow diagram (PFD) as shown in Figure 1.  Figure 2. CW`s waste water process flow diagram (PFD) 2.2. Methodology 2.2.1. Preliminary investigations Determining optimal combination of easily accessible adsorbents, with an accentuation on their natural origin was the primary goal of preliminary investigations. In preliminary investigations properties of two matal-complex dyestuff: 1. cupper (phtalocyanine dye) and 2.chromium complex, considering the possibility of their removal from waste waters, were investigated. Laboratory model was designed as a vertical column, 19cm high, 14 cm in diameter and 3967,39cm3 volume, with an outlet valve at the bottom of the column. Columns have been filled with various biological materials, which purifying properties were investigated, also. Those materials were: fine sand (grain size 0,5-1mm), sand (grain size 1-4 mm), gravel (grain size 8-16mm) and coarse gravel (grain size 32-64 mm) - of varying mass ratio. Geo textile filter: PP (surface mass 500 g/m2, thickness (20 N) 3,70 mm), has been used as a last filter component, placed at the bottom of the column (Fig.3). Purpose of this last component was to avoid burdening and clogging water pumps with small particles, which may occur in full scale pilot project purifying.  Figure 3. Simulated wetland 2.2.2. Construction of wetland system A Wetland System for the purposes of Textina`s textile factory dye-house waste waters purifying has been designed and constructed in Ajdova ina, Slovenia. The pilot system (Fig. 4 and 5) was designed on the basis of hydraulic loads of 1 m-3d and pollution loads. The new system consists of three beds. Both bed A and bed B are 5 m long and 4 m wide while the dimensions of the bed C are 5 X 8 m, in total 80 m2. Figure 5 shows the scheme of the system and its longitudinal cross-section. The bottom of both beds was fortified with a 2 mm thick HDPE foil was placed on the bottom to ensure impermeability. The water level was regulated with the valve at the outlets of the beds. Beds were planted with Phragmites australis with 5 clumps m-2, transferred from an old pilot plant. The actual retention time, measured by the electric conductivity was 40 hours by the hydraulic flow 1l/min. The outflow was in the nearby stream. Media consist of gravel and sand and are composed as follows: bed A and B: fine sand, grain size 1/4 mm sand, grain size 4/8 mm; ratio: 50 % : 50% bed C: fine sand, grain size 1/4, 8/16 mm gravel, grain size 32/64 mm; ratio: 42%:42%:16%  Figure 4. CW pilot system  Figure 5. Scheme of the system Performance of purifying method has been evaluated by investigation of the following parameters: pH Electrical conductivity Chemical Oxygen Demand (COD), ISO 5220 B Biochemical Oxygen Demand (BOD5), EN 1899-2 Total Organic Carbon (TOC), ISO 5310 Special Absorbance Coefficient (SAC), ISO 7887 Absorbable Organic Halogens (AOX), EN 17025 Cl- acc. Mohr 3. RESULTS AND DISCUSSION 3.1. Preliminary investigations Obtained SAC value (Fig. 6 and 7) for chosen dyestuff suggest great decolourisation and significant change in colour intensity, which indicates that dyestuff does not remain in waste waters being disposed or reused .  Figure 6. SAC values for cupper metal-complex dyestuff  Figure 7. SAC values for chromium metal-complex dyestuff Electrical conductivity values (Tab.1.) obtained after treatment in CW indicate significant salt removal and lowering values from about 100 mS to approximately 30mS, which amounts to a decrease of about 70 %. It is also important to notice how two CW systems do not show same electrical conductivity values measured before treatment processes, which was excepted due to the fact that CW is a system containing natural adsorbents and that the values obtained are not likely to be repeated on the another similar system even though the same mass of adsorbents was used when treatment media was built. Table  SEQ Table \* ARABIC 1. Conductivity of coloured waste waters Measurement stepsDyestuff groupCu complexCr -complexI. Before treatment in CWk [mS/cm]k [mS/cm]Dyestuff solution + 60 g/l NaCl 100,3100,5II. After treatment in CW for 3 hours period of timeDyestuff solution 0,25g/l + 60 g/l NaCl23,029,6Rinsing with 400ml of water38,335,6Rinsing with additional 400ml of water21,728,6 3.2. CW pilot system Measured values of industrial waste water entering the purifying process (Tab.2) are typical for waste waters obtained after dyeing process. Additional investigations were made in order of describing what would roughly be called a nitrogen cycle, which is along with the total amount of phosphorus a very important link in a unified eco-cycle of CW. Low values of ammonium, nitrate and nitrite suggest that waste water was obtained by mixing dye-house waste water with fecal waste waters. Table 2. Industrial dye-house waste wat. characterization ParametersValuespH Electrical conductivity (mS/cm) SAC (436 nm, 525 nm, 620 nm) COD (mg/l O2) BOD5 (mg/l O2) TOC (mg/l C) AOX (mg/l) Cl- (mg/l) NH4+ (mg/l) NO3- (mg/l) NO2- (mg/l) Total P (mg/l)7,16 2,42 34 / 100 / 5 1379 320 425 1080 512 2,15 0,11 0,17 4,32 Fig. 8 and 9 exhibits results obtained after purifying. Water flow of only 1l/m gave the most efficient results (reduction efficiency of over 90% for all parameters measured). However, increase of water flow to up to 5 l/min did not significantly reduce systems efficiency (parameters were within legally permitted). Further increase of water flow would additionally improve cost benefit of the system presented, but it gave unsatisfactory results concerning maximum allowed values. Parameter BOD5 was most influenced by the increase in water flow.  Figure 8. Characterization of purified industrial dye-house waste water (OUTLET) Colour reduction efficiency was measured through calculation of SAC (special absorption coefficient) values (measured at wave lengths of 436, 525 and 620nm). Results show (Fig.9) how colour reduction efficiency significantly decreases with the increase in water flow, exhibiting lowest SAC value at water flow of 10 l/min and wave length of 620 nm.  Figure 9. CW colour reduction efficiency for industrial dye-house waste water (OUTLET) pH levels have been measured throughout the whole purifying process and didnt exhibit major fluctuations (around 7,3). 4. CONCLUSION Construction of wetland was preceded by preliminary investigations, an imperative step of the project, used in order to predict the behavior of full scale model. Best results of preliminary investigations were obtained by assembling treatment media adsorbents accordingly to real geological profiles. 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Although, greater efficiency was obtained with lesser hydraulic load it exhibited poor cost benefit, which led to conclusion how hydraulic load of 5 l/min was optimal, regarding purifying efficiency vs. cost benefit. Full scale constructed wetland pilot project, described in the paper, is the first scientific approach to resolving dye-house wastewaters problem in the region. Secondary goal of the project was to educate people in the areas where water isnt recycled within a closed water cycle. Acknowledgements We thank Company for Applied Ecology - Limnos, Slovenia. This paper is a continuation of our cooperation within Eureka Textilwet E!2983 project. 5. REFERENCES Braux A., (2005), Wetland ecological and compliance assessments in the San Francisco Bay Region, California, USA. Environ. Manage, 74, 217-220 Brown D. S., (1994), Constructed wetlands in the USA. Water quality International. 4, 24-28 Griessler-Bulc T., Golob V., Parac-Osterman ., Sutlovi A., uraaevi V., (2005), Use of Wetland for Dyehouse Waste Waters Purifying Purposes - Ajdova ina, Slovenija (Research within Eureka Textilwet E!2983 Project), Proceedings of 1st EMCO workshop, Dubrovnik, Barcelo (Ed.), Dubrovnik, Faculty of Chemical Engineering and Technologies, Zagreb, 105-106 Parac-Osterman ., uraaevi V., (2005), Biological Treatment Of Coloured Waste Water Using Wetland System, Proceedings of 5th International Istambul Textile Conference, Istanbul, CD 79BCNOVWy:TVdfv́ƂȂւ؂ڂ{rg_hQLmH sH h h-imH sH h-;\mH sH h \mH sH h h-i6\mH sH h h-i6H*mH sH h h-i6mH sH h h 6mH sH ht>mH sH ht>h 6mH sH ht>h 6]mH sH h3mH sH ht>h mH sH hhmH sH ht>h-imH sH ".ŒČȌʌΌЌԌ֌ڌ܌ތh]h$a$ $d 7$8$a$gd-;$a$gd-;$d^a$gd-;ڂ\`~؃<@XZhjl܊ $,.‹:<>¹¹蘌{i[{Pht>h>KmH sH hhB*\mH phsH #ht>h-i6B*\mH phsH  ht>h-iB*\mH phsH h3B*mH phsH ht>h-iB*mH phsH h3mH sH ht>mH sH Uh-;6mH sH ht>h 6mH sH ht>h 6]mH sH h h-;6mH sH ht>h mH sH ht>h \mH sH Parac-Osterman ., Sutlovi A., uraaevi V., (2006), Study Of Purifying Textile Waste Water In Wetland System, Proceedings of AUTEX, Raleigh, SAD, CD Parac-Osterman ., Sutlovi A., uraaevi V., Griessler-Bulc, T., (2007), Use of Wetland for Dye-house Waste Waters Purifying Purposes. 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