Bioresource Technology 98 (2007) 436441

Short Communication

Surface ow constructed wetland for heavy oil-produced water treatment

G.D. Ji
b

a,*

, T.H. Sun b, J.R. Ni

a Department of Environmental Engineering, Peking University, Beijing 100871, PR China The Liaoning Provinces Key Laboratory of Environmental Engineering, Shengyang University, Shenyang 110044, PR China

Received 12 September 2005; received in revised form 18 January 2006; accepted 19 January 2006 Available online 10 March 2006

Abstract Heavy oil-produced water from China Liaohe Oileld was puried in a surface ow constructed wetland (SFCW) during a 3-yr eld experiment. Treatment showed high mean removal eciencies of 80%, 93%, 88% and 86% for COD, oil, BOD and TKN, respectively for reed bed #1 and 71%, 92%, 77%, and 81% for COD, oil, BOD and TKN, respectively for reed bed #2. The results also showed that in the third year of the systems operation, the oil-produced water had mainly positive impacts on the reeds health parameters. Thus, reed can be used as a feasible wetland macrophyte for treating such wastewater, and this SFCW system can operate for a long time. 2006 Elsevier Ltd. All rights reserved.
Keywords: Surface ow constructed wetland; Heavy oil; Produced water; COD

1. Introduction Heavy oil-produced water is separated during crude oil dehydration. Such wastewater is enriched with dissolved recalcitrant organic compounds such as polymers, surfactants, and heavy oil, with a viscosity >100 mPa S (Wan and Luo, 1998). In China, a large amount of such wastewater was recycled and/or discharged either partially or completely in various environments during the long era of oil extraction. It has been reported that currently in Chinas Liaohe Oileld, approximate 20 million m3 of such wastewater is annually discharged into nearby Liaohe River (Ji et al., 2002b, 2004). This has become a big environmental problem throughout the development of the petrochemical industry. Physical, chemical, and biological technologies have been developed to treat oil-produced water and restore environmental quality. However, their costs are high and most of them are dicult to use under
Corresponding author. Tel.: +86 010 62755914 87; fax: +86 010 62756526. E-mail addresses: jiguodong@sina.com, jiguodong@iee.pku.edu.cn (G.D. Ji). 0960-8524/$ - see front matter 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.biortech.2006.01.017
*

eld conditions. It remains necessary to study natural, simple, and cost-eective techniques for treating such wastewater, such as constructed wetlands. In recent years, the petroleum industry has shown interest in using constructed wetlands (CW) to manage wastewater at a variety of installations, including reneries, oil and gas wells, pumping stations, and sites of oil contaminated soil (Harris et al., 1999; Knight et al., 1999). These constructed wetlands can supply predictable water quality if they are properly designed and maintained. However, studies involving oil-produced water treatment by surface ow constructed wetland (SFCW) are scarce in China. Thus, the objectives of the present study was to determine the treatment eciency of the SFCW system, especially for COD, and to evaluate the eect of oil-produced water on reed health under eld conditions. 2. Methods 2.1. Design of SFCW system The study site is located in the Liaohe Oileld, near the Delta wetland in Chinas northeast region (12205 0 E,

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4105 0 N). Due to the temperature of the produced water at about 60 C, this wastewater was pre-treated in a facultative waste stabilization pond (WSP). The CW was built downstream from the WSP. The pilot scale SFCW consisted of two reed beds and a control bed, which were parallel arranged (1687.5 m2 total surface area, each 75 m long, 7.5 m wide, with a depth of 0.25 m and a slope of 0.2%). Wastewater was pumped from the lower WSP to the upper two series of reed beds. The inow device was a conveyance slot and the outow device a triangular overow weir. Previous monitoring indicated that COD concentrations in the samples at the outlet of WSP ranged from 300 to 600 mg l1, with an average concentration of 400 mg l1. Thus, based on experiences of previous experimental subsurface wetlands (Ji et al., 2002b) and the above mentioned COD concentrations, targeted COD loading rates in this study were designed at 13.3 and 26.7 g m2 d1 for reed bed #1 and reed bed #2, respectively. Corresponding hydraulic loading rates (HLR) were 18.75 (reed bed #1) and 37.5 m3 d1 (reed bed #2). Hydraulic retention times (HRT) were 15 (reed bed #1) and 7.5 d (reed bed #2). The control bed was left without wastewater, but was lled with upstream Liaohe River water to evaluate the eects on reed health with and without produced water. In March of the rst year, the wetland was planted with common reeds, and in April of the same year, the two series of reed beds were lled with wastewater. Because the inow equipment was not winterized, operation was impossible during the frost period (early December to late March). Due to the poor quality of produced water and the potential toxicity to plants and microorganisms, the system had a long start-up period of two years, whereas no data were recorded. In the third year, the two series of reed beds were lled with wastewater in April 1st (day 1), then, we sampled and analyzed the treatment eectiveness of the SFCW system and the impact of such wastewater on reed health. 2.2. Sampling frequency and analytical techniques Water sampling was carried out every two weeks between 11:30 and 12:30 from day 58 to day 163 (i.e., from May 28th to September 11th of the third year). The samples were taken from four points: the inlet to WSP, the outlet of WSP (i.e., the inlet to reed beds), the outlet of reed

bed #1, and the outlet of reed bed #2. The treatment eciency of SFCW was determined by using following parameters: pH, COD, mineral oil, biological oxygen demand (BOD5), total Kjeldahl nitrogen (TKN), and total phosphorus (TP). The pH value was measured with a model pHs25 m by the glass electrode method. COD, as a measure of the organic strength of the wastewater, was determined by the potassium dichromate method. Mineral oil was measured with the ultraviolet spectrometer in petroleum ether extract at the wavelength of 254 nm. BOD5 was determined by measuring the amount of oxygen absorbed by a sample of wastewater in the presence of microorganisms within ve days at 20 C. TKN and TP were determined by standard Kjeldahl and molybdenum blue methods, respectively. The above-mentioned parameters were measured according to the Standard Method for Examination of Water and Wastewater (Standard Method for the examination of water and wastewater editorial board, 1993). Reed samples were taken from all reed beds, as well as the control bed. During the growing season, every ten to fteen days, 3060 reed plants were randomly selected to survey their numbers of leaves and their heights. Other parameters, such as cellulose, lignin, pentose, length/width ratio of cellulose, and the aboveground dry biomass, were determined by harvesting several randomly selected 1 m2 plots. After cutting the plants into about 10 cm pieces, the reed was dried at 105 C and weighed to identify their aboveground dry biomass (g m2). Other indices were determined according to standard methods (Chen and Yu, 1989). 3. Results 3.1. Water quality and performance eciency During the sampling periods, water samples were collected and analyzed for each of pH, COD, BOD5, TKN, TP, and mineral oil. Table 1 is a summary of the monitoring data for two reed beds. The average pH values of the reed beds were 7.88 (inuent), 7.77 (euent of reed bed #1), and 7.63 (euent of reed bed #2) (Table 1), indicating that pH was not aected by SFCW. However, the results showed that SCFW caused a decrease of COD. The mean COD concentration at the euent of the two reed beds

Table 1 Mean (SD) of monitoring parameters data from May to September of the third year (all mg l1, except for pH) Indicator Reed beds inuent Reed beds euent #1 pH COD BOD5 Mineral oil TKN TP 7.88 0.40 390 124 32.1 8.5 20.0 4.6 11.6 1.6 0.07 0.03 7.77 0.32 77 10 3.9 2.2 1.4 1.1 1.6 1.3 0.18 0.11 #2 7.63 0.24 114 12 7.3 1.3 1.8 1.5 2.3 2.1 0.14 0.09 Standard values for rst class of waste water discharge (State Environment Protection Administration of China (1998)) 69 100 30 10 10 0.5

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were 77 (reed bed #1) and 114 mg l1 (reed bed #2) (Table 1). Removal eciencies (80% for reed bed #1, 71% for reed bed #2) remained constant over time (Table 1, Fig. 1). Since the 2nd class of the national wastewater discharge standard for COD for the Liaohe Oileld is below 150 mg l1 (State Environment Protection Administration of China, 1998), the euent quality of SFCW can meet this standard. The euent quality in reed bed #1 was within the rst national standard (100 mg l1). Although mean BOD5 concentration at the inlet of the reed beds was quite low (32.1 mg l1), mean BOD5 concentrations at the outlet were even lower (3.9 mg l1 for reed bed #1 and 7.3 mg l1 for reed bed #2). Furthermore, high removal eciencies of 88% for reed bed #1 and 77% for reed bed #2 remained constant over time (Table 1, Fig. 1). Mineral oil is also a characteristic parameter of such wastewater. Its discharge standard in the Liaohe Oileld was below 10 mg l1 (State Environment Protection Administration of China, 1998). Mineral oil concentrations at the euents of the treatment wetland were signicantly lower than at the inuent during the third year. Inuent mineral oil concentrations ranged between 15 and 30 mg l1, while those gures at the euents were
700 600 500
COD (mg l-1)

1.4 mg l1 for reed bed #1 and 1.8 mg l1 for reed bed #2. The mean removal eciencies were 92.8% (reed bed #1) and 91.6% (reed bed #2) (Table 1, Fig. 1). TKN concentrations in the inuent ranged between 10 mg l1 and 20 mg l1, with a mean TKN concentration of 11.6 mg l1. Mean euent concentrations were 1.6 mg l1 (reed bed #1) and 2.3 mg l1 (reed bed #2). Mean removal eciencies were 86% and 81% for reed bed #1 and #2 respectively (Table 1, Fig. 1). TP concentrations in the treatment wetland euents were higher than TP concentration in the inuent throughout the sampling period (Table 1). 3.2. Reed health parameters At the end of the experiment, the mean height of reed was 208 cm for reed bed #1 and 182 cm for reed bed #2, which was slightly lower than 221 cm found in the control bed. The mean number of reed leaves in the reed beds and the control bed were similar, 20.0 for reed bed #1, 21.7 for reed bed #2, and 21.1 for control bed. Reed biomasses were 751 g m2 (reed bed #1) and 657 g m2 (reed bed #2), in contrast to the control bed, where the reed biomass of
70 60 50
BOD5 (mg l -1)

400 300 200 100 0 58

40 30 20 10 0 58

79

100 121 Time (days)

142

163

79

100 121 Time (days)

142

163

30 27 24
Mineral oil (mg l-1)

21 18 15
TKN (mg l-1)

21 18 15 12 9 6 3 0 58 79 100 121 Time (days) 142 163

12 9 6 3 0 58 79 100 121 Time (days) 142 163

Fig. 1. Time variation of oil-produced water quality for COD, mineral oil, BOD5, and TKN (wetland inuent (m); reed bed #1 euent (j) and reed bed #2 euent (s). Bars indicate SD.

G.D. Ji et al. / Bioresource Technology 98 (2007) 436441 Table 2 The health parameters of reeds in reed bed #1 and #2 and control bed (mean SD) Indicator Reed bed #1 Reed bed #2 Control Number of leaves 20.0 1.2 21.7 1.5 21.1 1.9 Plant height (cm) 207 19 182 15 221 16 Biomass (g m2) 751 23 657 16 627 13 Cellulose (%) 38.41 0.42 41.36 0.51 38.92 0.44 Lignose (%) 19.28 0.47 19.89 0.62 19.37 0.55 Pentose (%) 18.20 0.45 18.70 0.57 17.00 0.52 Length:width ratio of cellulose 1.33 0.14 1.36 0.15 1.27 0.12

439

Width of cellulose (lm) 11.50 1.16 12.50 0.93 13.60 1.05

the corresponding period was only 620 g m2 (dry weight at 105 C). For other indices at 215 days (i.e., the harvesting season), see Table 2. 4. Discussion 4.1. Treatment eectiveness of SFCW The results indicated that this SFCW system could remove mineral oil eectively. Plants in the wetland have a natural mechanism for pumping air via their root systems. The root area provides an oxygen-rich environment, which supports a range of aerobic bacteria (Brix, 1994). Furthermore, a range of anoxic and anaerobic microbial processes occurs within wetlands (Reddy and Patrick, 1984). These biological processes promote the degradation of mineral oil. Mineral oils in wetlands are also subjected to physical processes such as evaporation, leaching, sorption of soil particles, and sedimentation (Mashauri et al., 2000), which can also ensure a high removal eciency of mineral oil. It should be pointed out that seasonal variation of outlet mineral oil concentrations may be due to variations in temperature, biomass of reed, and the types and quantities of microorganisms, which needs to be further studied. SFCW system could reduce mean COD concentration at the euent of the two reed beds to 77 mg l1 (#1) and 114 mg l1 (#2), respectively. Furthermore, the mean removal eciency of reed bed #1 was 10% higher than that of reed bed #2. This indicated that removal eciencies decreased with higher HLR. COD removal loading rate (RLR) was also calculated, which was equal to the removed COD quantity divided by the reed bed surface area. M Q S 0 S e A 1

where M is pollutant removal loading rate (g m2 d1); S0 is pollutant concentration at the inlet of reed bed (mg l1); Se is pollutant concentration at the outlet of reed bed or national standard (mg l1); Q is the ow rate (m3 d1); A is the surface area of reed bed (m2). Results showed that the 18.4 g m2 of mean COD RLR for reed bed #2 was higher than the 10.4 g m2 for reed bed #1, indicating that COD RLR increased with higher HLR. Thus, HLR of reed bed #1 ensured better euent quality (the rst national standard) than reed bed #2, whereas RLR of reed bed #2 could treat more wastewater at the second national standard and obtain a higher economic

value than that of reed bed #1. These ndings provided useful information on wetland design and operation. In previous studies, the ratio of BOD5:COD = 0.3, as indicative limitation for wastewater biodegradation was thought as the limiting factor for inuent quality of constructed wetlands (Sun, 1997). Although in this study the mean BOD5:COD ratio of produced water was only 0.08, the purication eciency of wetlands was high. Wetlands composed of substrates-vegetables-microorganisms have a complicated mechanism of purication (Ji et al., 2002b). Brix (1994) and House (1999) showed that substrate ltration, plant sorption, substrate adsorption, and the settling process in a wetland removed suspended COD in wastewater. However, in the present study, the produced water owed from the surface of the substrate, which resulted in ltration, but had no impact on COD removal. Thus, the last three processes played an important role in suspended COD removal. For soluble COD, some previous studies have demonstrated that substrate, plants adsorption, and plant sorption have little eects on COD removal (Ji et al., 2002a; Vymazal et al., 1998). It is aerobic oxidation that plays an important role in removal of soluble COD (Kadlec et al., 2000). Hutchinson et al. (2001) found the optimal ratio of C:N:P in the greenhouse experiment on phytoremediation petroleum hydrocarbons to be 100:2:0.2, which was similar to the mean ratio of COD:TKN:TP in the wastewater in present study (560:17:1). Thus, produced water could provide nitrogen and phosphorus for COD removal in wetlands. Reduction of TKN could be due to the absorption by plant and microbiological biochemical activity (Hill et al., 1997; Jing et al., 2001; Juren, 1999). At 121 days (i.e., July 30 of the third year), TKN reached the lowest value (Fig. 1). Possible reasons were that during the peak reed growth period of late Julyearly August, the reed strongly adsorbed N. Then high microbial activities were obtained, resulting in the minimum value of TKN. 4.2. Reed health indices The height of the reeds in reed beds was reduced slightly than that in the control. However, the biomass of the reeds in reed beds was higher than that in the control, and greater biomass was observed with lower HLR beds. Previous studies indicated that low concentrations of mineral oil stimulated vegetable growth (Gao, 1986). Present results conrmed these observations. The number of leaves, as an important index of plant growth, reected plant

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photosynthesis and transpiration, i.e., metabolism ability (Li et al., 1996). The higher number of leaves, the more vigorous plant growth occurs (Li and Chen, 2000). Previous studies also found that the adverse eects of oil on vegetation ranged from short-term reductions in photosynthesis to mortality (Lu et al., 1987; Baker, 1970; Delaune et al., 1979; Pezeshki et al., 2000; Scrimshaw and Lester, 1996). However, in this work, no signicant dierences in the numbers of leaves were observed between reed beds and the control bed, indicating that after a 2-yr start-up period, the reed exhibited a strong tolerance to the oil-produced water, resulting in constant photosynthesis and transpiration. General speaking, the ranges of the reed quality indices are 3842% of cellulose (the higher the gure, the better the quality); 1819% of lignose (the lower the gure, the better the quality); 1619% of pentose, length/width ratio of cellulose between 1.0 and 1.2; 1014 lm width of cellulose for better quality (Chen and Yu, 1989). Results indicated that cellulose and pentose were in normal scope in all beds, and the values of reed bed #2 with higher HLR were superior to the values of reed bed #1 with lower HLR. Lignose in all beds were higher than the normal scope, but they were similar in both the reed beds and the control bed. Although the width of cellulose in reed beds was lower than those in the control bed, all of them were within the normal range. Length: width ratios of cellulose in reed beds were lower than that of the control bed. These results indicated that reed health indices in reed beds were within the normal scope, or superior to those in the control bed, showing that heavy oil-produced water had a positive eect on reed health. 5. Conclusions In this pilot study for the rst time a surface ow constructed wetland located in Liaohe Oileld was used for treating heavy oil-produced water. The results demonstrated that SFCW could remove large amounts of COD contained in produced water, and the euent quality of the system remained stable. The ndings HLR and RLR of COD could be used to provide useful information on design and operation of SFCW technology. Results also indicated that reed could be a feasible wetland plant for treating heavy oil-produced water, and the SFCW system could be operated for a long time. Acknowledgements The study was funded by the National Natural Science Foundation of China (20507001) and the National High Technology Research and Development Program of China (863 Program) (2004AA649360). The authors also thank Dr. Silke Wieprecht from Bundesanstalt Gewa sserkunde German Federal Institute of Hydrology for providing detailed advice that contributed to improvements and renements in the paper.

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