Ecological Engineering 41 (2012) 8–12 Contents lists available at SciVerse ScienceDirect Ecological Engineering journal homepage: www.elsevier.com/locate/ecoleng Short communication Vertical oxygen distribution trend and oxygen source analysis for vertical-flow constructed wetlands treating domestic wastewater Jianfeng Ye a,∗ , Liang Wang b , Dan Li a , Wei Han c , Chao Ye c a Shanghai Academy of Environmental Sciences, Shanghai 200233, China Shanghai Advanced Research Institute, the Chinese Academy of Sciences, Shanghai 201210, China c College of Environment, Hohai University, Nanjing 210098, China b a r t i c l e i n f o Article history: Received 29 June 2011 Received in revised form 9 November 2011 Accepted 10 December 2011 Available online 1 February 2012 Keywords: Constructed wetland Oxygen concentration Atmospheric reoxygenation Domestic wastewater Vertical-flow constructed wetland (VFCW) a b s t r a c t To improve nitrogen removal performance in vertical-flow constructed wetlands (VFCWs) and promote their application in domestic wastewater treatment in China, it is important to identify the reoxygenation sources, their contribution weightings and the oxygen distribution profiles in the VFCW substrates. This study indicated that dissolved oxygen (DO) levels rise at first and then drop in the VFCWs vertically from top to bottom in the VFCWs treating domestic wastewater. There were other sources of oxygen supply to the wastewater in the VFCWs, especially in the upper portion of the VFCWs. In treating domestic wastewater, atmospheric reoxygenation is the main oxygen source for the VFCWs, contributing more than 99.9% of the total oxygen supply. Approximately 50% of atmospheric reoxygenation is supplied to 0–10 cm below the wastewater distribution system in the VFCWs. Over 99.8% of the oxygen consumed is used for organics degradation and nitrification. In this study, oxygen was mainly consumed in organics degradation in the upper 0–40 cm of the VFCWs and nitrification was dominant in the lower part. © 2012 Published by Elsevier B.V. 1. Introduction Constructed wetland technology was developed in 1970s as an emerging wastewater treatment technology (Kadlec et al., 2006). This technology has been widely applied to domestic wastewater treatment in rural areas and medium-small towns in China due to its easy maintenance, low cost, and energy savings (Verhoeven and Meuleman, 1999; Kivaisi, 2001; Li et al., 2009). Vertical-flow constructed wetland (VFCW), a type of constructed wetlands, has gained popularity in China owing to its compact size and enhanced pollutant removal capacity (Brix and Arias, 2005). However, unsatisfactory nitrification performance has been reported for single-stage VFCWs usually after 1–3 years’ running (Claudiane et al., 2006; Li et al., 2008). It has been concluded that insufficient oxygen supply to the wetland substrate due to configuration design impairs the ammonia oxidation reactions (Yan et al., 2006; Ke et al., 2008; Lee et al., 2009; Allen et al., 2010). This hypothesis has not been validated by any actual experiment data. Nevertheless, according to many studies on Radial Oxygen Loss (ROL) and wetland plant root zoon reoxygenation sources (Brix, 1987; Wolfgang et al., 1992; Sasikala et al., 2009), oxygen ∗ Corresponding author. Tel.: +86 21 64085119; fax: +86 21 64085119. E-mail addresses: [email protected], [email protected] (J. Ye). 0925-8574/$ – see front matter © 2012 Published by Elsevier B.V. doi:10.1016/j.ecoleng.2011.12.015 transportation is an active energy-consuming act of plants and the oxygen transporting rate by ROL is not negligible (Shimp et al., 1993; Dunbabin et al., 1998). Studies indicate that if organic pollutant concentrations of the wastewater are elevated, the oxygen concentration will decrease substantially in constructed wetlands without plants, but remain within the aerobic zone in wetlands with plants. The oxygen transported by plants is able to sustain aerobic microbes’ metabolism (Kadlec et al., 2006), which contradicts with the hypothesis that ammonia oxidation reactions are impaired by insufficient internal oxygen supply. In order to improve nitrogen removal performance in VFCWs and promote their application in domestic wastewater treatment in China, it is critical to identify the reoxygenation sources, their contribution weightings and the tendency of oxygen distribution in the VFCW substrates. Data gained in this research can be used to improve the wetland configuration and system designs. 2. Materials and methods 2.1. VFCW reactors Six identical reactors simulating VFCWs were divided into two groups (Group A and B) in this study. Both groups are composed of three duplicate reactors. The dimensions of the reactors are 1.5 m (L) × 0.5 m (W) × 1.4 m (H). The reactors were filled with a coarse sand substrate to 120 cm in height. The d10 and d50 diameters of the substrate are 0.25 mm and 0.60 mm, respectively. The uniformity coefficient (Cu ) of the substrate is 3.2 and the permeability coefficient is 1.27 × 10−2 cm s−1 . Wastewater distribution systems were installed at 10 cm below the surface level. Wastewater harvesting systems were laid at 0.5 cm above the reactor bottoms, which were 40 cm below the distribution systems. Wastewater distribution and harvesting systems were made of serrated PVC pipes of 20 mm in diameter with holes for wastewater distribution/harvesting every 12.5 cm along the pipes. Each reactor has six wastewater and substrate sampling points at 0 cm, 10 cm, 20 cm, 40 cm, 60 cm and 80 cm below the wastewater distribution systems. The height of the wastewater distribution systems is set to be 0 cm in this paper hereafter. Phragmites australis were planted on top of the substrate in the six reactors with a density of 4 stems·m−2 . Wetlands height / cm J. Ye et al. / Ecological Engineering 41 (2012) 8–12 9 0 0 20 20 y=94.39-42.62x 2 R =0.86(n=6) 40 60 60 y=104.90-21.83x 2 R =0.92 (n=6) 80 3 2.2. Experiment settings and sampling method 2.3. Influent water quality and hydraulic loads Domestic wastewater was used as influent for the VFCW reactors in this study. The influent was introduced continuously without extra pressure. The hydraulic load was 0.5 m3 m−2 d−1 for Group A reactors, and 0.3 m3 m−2 d−1 for Group B reactors. The water quality values were measured daily in influent water: DO is 0.27 ± 0.19 mg L−1 (range: 0.07–0.7), pH is 7.37 ± 0.24 (range: 6.9–7.9), SS is 113 ± 25 mg L−1 (range: 64–192), COD is 225 ± 72 mg L−1 (range: 133–310), TP is 1.80 ± 0.49 mg L−1 (range: 1.2–2.7), NH4 + -N is 25.0 ± 6.63 mg L−1 (range:13.0–39.7). 80 -2 -1 0.5m .m .d 3 -2 -1 0.3m .m .d 100 The experiment was conducted from June to November 2009. The VFCW reactors were placed outdoor where temperature ranged from 24.0 to 37.3 ◦ C, and sunlight intensity was about 1480–4450 lx. The reactors were run for one month to stable status before wastewater and substrate samples were taken. Wastewater samples were collected via vacuumed hoses connected to wastewater sampling points. Substrate samples were taken at each sampling points by using a Luoyang shovel, which should be inserted into the reactors at a 45 cm distance. Each sample should be mixed up completely. 40 100 120 120 0 1 2 3 4 5 6 DO levels in wastewater/mg.L-1 Fig. 1. DO distribution in wastewater in VFCW reactors. spectrophotometer(Shimadzu). The oxygen supply volumes can be determined by the difference between the ␣-naphthylamine concentrations of the two sample batches excluding the values of blank duplicates (Colmer, 2003). The biofilm mass was tested by an ultrasonic and chemical stripping method (Ye et al., 2008). The weight loss during the ignition is considered as the volatile biofilm mass. Biological oxygen demand (BOD) concentrations were tested by a multiple dilution method. Ammonia nitrogen concentrations were tested using the Nesslers reagent colorimetric method. Nitrite nitrogen levels were tested by spectrophotometry. Nitrate nitrogen levels were tested by ultraviolet spectrophotometry. DO levels were tested with a HACH Portable DO Meter. All samples were analyzed according to applicable Chinese national standards (MEPC, 2002). 3. Results and discussion 2.4. Test methods 3.1. Oxygen distribution and transformation Test of radial oxygen loss from reed root was performed as follows: after analyzing the DO in wastewater samples, the intact reed plants were taken out and cleaned with deionized water. Residual deionized water on the reeds was removed with blotting paper. Each reed plant was dipped in a separate sealed cylinder container with a mixture of 2.0 L of 40 mg L−1 ␣-naphthylamine solution and 2.0 L of 0.1 M phosphoric acid buffer solution. The containers were shaken and left stationary to eliminate the influence of DO in the solution and the air in the containers. After being kept stationary for 5 min, 2 mL of the solution was taken out from each container and put into individual 25 mL volumetric flasks (batch 1). The cylinder containers were then sealed with silicon, kept indoor with temperature of 23–28 ◦ C, and shaken every hour. After 5 h, 2 mL of the solution was taken from each of the containers and transferred to separate 25 mL volumetric flasks (batch 2). 10 mL of deionized water, 1 mL of 1% aminobenzene sulfonic acid solution and 1 mL of 100 mg L−1 sodium nitrite solution was added into each of the volumetric flasks for both sample batches. The volumetric flasks were then shaken for 5 min for chromo generation of the mixed solutions and filled with deionized water. Within 20–60 min, the ␣-naphthylamine concentrations in the solutions in all the flasks were tested with a 510 nm band using UV-1700 3.1.1. Vertical oxygen distribution in wastewater Curves of wastewater DO levels in VFCW reactors with different hydraulic loads are shown in Fig. 2. As shown in Fig. 1, vertically from top to bottom, DO levels in the wastewater increased from 0 to 10 cm below the wastewater distribution systems and then decrease further below. With various hydraulic loads in this study, the DO levels in wastewater at 10 cm below the wastewater distribution systems were tested to be 18 times and 33 times of the ones in the wastewater influents. However, from 10 cm below the wastewater distribution systems to further below, the DO levels in wastewater decreased gradually, with Group B having a rate 1.95 times that of Group A’s. The biofilm mass and volatile biofilm mass were analyzed and the results are illustrated in Fig. 2. Based on the above analysis, it was found that from 10 cm below the wastewater distribution systems, DO levels in wastewater have positive correlations to biofilm mass at the same height of the reactors. The correlation coefficient of DO levels in wastewater to biofilm mass for Group A and Group B is 0.899* (p < 0.015) and 0.941* (p < 0.005) respectively. The correlation coefficient of DO levels in wastewater to volatile biofilm mass for Group A and Group B is 0.709 10 J. Ye et al. / Ecological Engineering 41 (2012) 8–12 Wetlands of group B Wetlands height (cm) Wetlands of group A 0 0 0 0 20 20 20 20 40 40 40 40 60 60 60 60 80 80 80 80 100 100 100 100 120 120 0 40 80 120 160 120 120 0 40 80 -4 120 160 -1 Biological membrane quantity (10 mg.mLsubstrate) 0 20 40 60 0 20 40 -4 60 -1 Volatility biological membrane quantity (10 mg.mLsubstrate) Fig. 2. Vertical distribution of the biofilm mass and volatile biofilm mass. and 0.691, respectively. Therefore, it is concluded that beside the oxygen contained in the wastewater influent stream, there are other oxygen sources present (atmospheric reoxygenaration and ROL from plant roots), especially in the top section of the reactors. 3.1.2. Vertical distribution of oxygen transformation in wastewater Except for denitrification processes, the organic pollutants in wastewater are mostly degraded by aerobic microbes. The oxygen demands can be calculated using the following formula (Zhang, 2000): O2 = a BODr + b P (1) where a – oxygen demand for degrading every kilo of BOD5 , which valued 1.46; BODr – decreased BOD5 value in constructed wetlands; b – oxygen demand for sustain every kilo of active biofilm, which is 0.18 kg kg−1 ; P – active biofilm mass in every cubic meter of wetland substrate (kg m−3 ). Based on the biofilm mass analysis results in Fig. 2, the average oxygen demands for degrading organic pollutants in the two groups of VFCW reactors are calculated and listed in Table 1. The total oxygen demand for degrading organic pollutants for Group A reactors and Group B reactors is 77.328 g d−1 and 52.706 g d−1 , respectively. Removal of ammonia nitrogen is realized via nitrification. The oxygen demands for nitrification in the VFCW reactors are calculated and the results are summarized in Table 1. The average oxygen demand for nitrification for Group A and Group B was calculated to be 39.429 g d−1 and 58.844 g d−1 , respectively. 3.1.3. Analysis of vertical distribution of oxygen transformation DO in the wastewater is mainly used in degradation of organic pollutants and nitrification. The transformed oxygen amount is illustrated in Fig. 3. As shown in Fig. 3, oxygen demand is higher within 10 cm below the wastewater distribution systems than that of further below. The daily oxygen demand in Group A and Group B reactors within top layers was 56.332 g and 61.342 g, respectively, which accounted for 47.37% and 52.96% of their total oxygen demand respectively. Considering the vertical distribution profiles of oxygen concentration, oxygen is mostly consumed for organic pollutant degradation in upper portions of the VFCW reactors, and used mainly for nitrification in the lower portions. Oxygen consumed for organic pollutant degradation within the 40 cm below the wastewater distribution systems in Group A and Group B reactors accounted for 75.28% and 55.92%, respectively, of the total oxygen demand in the upper sections of the reactors, while nitrification oxygen demand accounted for 63.55% and 72.99%, respectively, of the total oxygen demand in the lower parts of Group A and Group B reactors. The percentage is correlated with the hydraulic loads of the wastewater influents. 3.2. Calculations of oxygen supply in VFCWs There are three oxygen supply sources for VFCWs: (1) DO in the wastewater influent, (2) ROL from the plant roots and (3) atmospheric reoxygenation. Oxygen losses are due to organic pollutant degradation, ammonia nitrification and DO in the wastewater effluent. According to law of mass conservation, the oxygen supply and consumption can be expressed with the following formula: Oself-in + Oplant + Oair = Oself-out + Oorg + Onitri (2) where Oself-in – DO in influents, g d−1 ; Oplant – ROL from plant roots, g d−1 ; Oair – atmospheric reoxygenation, g d−1 ; Oself-out – DO in wastewater effluents, g d−1 ; Oorg – oxygen consumed in organic pollutant degradation, g d−1 ; Onitri – oxygen consumed in ammonia nitrogen nitrification, g d−1 . DO in Group A and Group B reactor effluents were 0.21 ± 0.02 mg L−1 and 0.47 ± 0.07 mg L−1 , respectively. Influent DO was approximately 0.27 mg L−1 . Therefore, the wastewater brought J. Ye et al. / Ecological Engineering 41 (2012) 8–12 11 Table 1 Vertical distribution of average oxygen demand for organic pollutant removal and nitrification oxygen consumption. Depth in Group A reactors the Substrate (cm) Group B reactors BOD5 a (mg L−1 ) P (kg m−3 ) NO2 − -N NO3 − -N Oxygen demand for (mg L−1 ) (mg L−1 ) organic Pollutant removal (g d−1 ) Nitrification BOD5 a oxygen (mg L−1 ) consumption (g d−1 ) P (kg m−3 ) NO2 − -N NO3 − -N Oxygen demand for (mg L−1 ) (mg L−1 ) organic pollutant Removal (g d−1 ) Nitrification oxygen consumption (g d−1 ) 0–10 10–20 20–40 40–60 60–80 80–110 102 0 20 11 7 1 0.00140 0.00235 0.00225 0.00065 0 0 0.028 0.120 0.258 0 0.010 0.026 0 4.4 12.3 0 8.0 7.8 55.864 0.032 11.011 6.040 3.833 0.548 0.012 5.363 14.960 0.000 9.665 9.430 103 25 2 25 2 0 0.00255 0.00095 0.00085 0.0014 0.0009 0 0.469 0 0 0.040 0 0.160 21.9 0 2.9 8.5 0 15.2 33.870 8.225 0.680 8.250 0.681 0 26.639 0.000 3.503 10.281 0.000 18.421 Total 141 – 0.442 32.5 77.328 39.429 157 – 0.669 48.5 51.706 58.844 a Experiment results exclusive of the carbon consumed in denitrification processes. 0-10 Wetlands height(cm) Wetlands height(cm) 0-10 10-20 Wetlands of group A 20-40 40-60 Oxygen demends for nitrification Oxygen demends for organic degradation 60-80 80-110 10-20 Wetlands of group B 20-40 40-60 Oxygen demends for nitrification Oxygen demends for organic degradation 60-80 80-110 0 10 20 30 40 50 60 0 10 Oxygen demends(g.d-1) 20 30 40 50 60 70 Oxygen demends(g.d-1) Fig. 3. Vertical distribution of oxygen transformation in VFCW reactors. in 0.10 g d−1 and 0.06 g d−1 , respectively, of oxygen to Group A and Group B reactors and took out 0.079 g d−1 and 0.18 g d−1 , respectively, of oxygen from Group A and Group B reactor. ROL test results showed that the average total ROL from reed roots in Group A and Group B reactors was 11.6 ± 0.0029 mg d−1 and 10.5 ± 0.0024 mg d−1 , respectively. If all the ROL dissolved in the wastewater, the ROL supplied a maximum of 0.0116 g d−1 and 0.0105 g d−1 of oxygen to the Group A and Group B reactors. Based on Formula 2, with the hydraulic load being 0.5 m3 m−2 d−1 and 0.3 m3 m−2 d−1 , the total oxygen demand for Group A and Group B VFCW reactors were 116.836 g d−1 and 111.730 g d−1 , respectively. The contribution of ROL, influent DO and atmospheric reoxygenation can be calculated by backstepping from Formula 2. Atmospheric reoxygenation accounted for over 99.90% and 99.94% of the total oxygen supply for the Group A and Group B reactors. Therefore, the predominant oxygen source for VFCWs is atmospheric reoxygenation. 4. Conclusion Vertically from top to bottom, wastewater DO levels rise at first and then drop in the VFCWs treating domestic wastewater. DO levels in the VFCWs’ wastewater are positively correlated with the biofilm mass, which indicates there are other sources of oxygen supply to the wastewater beside dissolved oxygen in the influent, especially in the upper portion. This phenomenon is consistent with the hypothesis that atmospheric reoxygenation is the main oxygen source for the VFCWs. When treating domestic wastewater, atmospheric reoxygenation contributes more than 99.9% of the total oxygen supply to the VFCWs. Approximately 50% of atmospheric reoxygenation is supplied to the upper portion of the VFCWs, which is at from 0 to 10 cm below the wastewater distribution system. Over 99.8% of the oxygen consumed is used for organics degradation and nitrification. In this study, oxygen was mainly consumed in organics degradation in the upper 0–40 cm of the VFCWs and nitrification was dominant in the lower part (40–110 cm). Acknowledgements The authors would like to acknowledge the financial support from the National Natural Science Foundation of China (Grant No. 51108266), the Natural Science Foundation of Shanghai (Grant No. 11ZR1430800 and 08ZR1416400) and Open Foundation of State Key Laboratory of Hydrology-Water Resources and Hydraulic Engineering in China (Grant No. 2010490711). 12 J. Ye et al. / Ecological Engineering 41 (2012) 8–12 References Allen, J.G., Beutel, M.W., Call, D.R., Fischer, A.M., 2010. Effects of oxygenation on ammonia oxidation potential and microbial diversity in sediment from surfaceflow wetland mesocosms. Bio. Technol. 101 (4), 1389–1392. Brix, H., Arias, C.A., 2005. 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