Bioresource Technology 148 (2013) 334342

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Feasibility of bioengineered two-stages sequential batch reactor and ltrationadsorption process for complex agrochemical efuent
Pravin Manekar , Rima Biswas, Chaitali Urewar, Sukdeb Pal, Tapas Nandy
CSIR-National Environmental Engineering Research Institute, Nagpur 440 020, India

h i g h l i g h t s
 We investigated applicability of

g r a p h i c a l a b s t r a c t

BTSSBR as against SSBR for agrochemical efuent.  More than 90% of ammonia was removed in air stripper improving BTSSBR system.  BTSSBR system fends off competition between heterotrophic and autotrophic bacteria.  Air stripper, BTSSBR and ltration adsorption process treat agrochemical efuent.

Bioengineered

Single stage bio-oxidation process

BTSSBR process

a r t i c l e

i n f o

a b s t r a c t
In the present study, the feasibility of a bioengineered two-stages sequential batch reactor (BTSSBR) followed by ltrationadsorption process was investigated to treat the agrochemical efuent by overcoming factor affecting process stability such as microbial imbalance and substrate sensitivity. An air stripper stripped 90% of toxic ammonia, and combined with other streams for bio-oxidation and ltration adsorption. The BTSSBR system achieved bio-oxidation at 6 days hydraulic retention time by fending off microbial imbalance and substrate sensitivity. The maximum reduction in COD and BOD by heterotrophic bacteria in the rst reactor was 87% and 90%, respectively. Removal of toxic ammoniacal-nitrogen by autotrophic bacteria in a post-second stage bio-oxidation was 97%. The optimum ltration and adsorption of pollutants were achieved at a ltration rate of 10 and 9 m3 m2 h1, respectively. The treatment scheme comprising air stripper, BTSSBR and ltrationadsorption process showed a great promise for treating the agrochemical efuent. 2013 Elsevier Ltd. All rights reserved.

Article history: Received 27 June 2013 Received in revised form 23 August 2013 Accepted 25 August 2013 Available online 3 September 2013 Keywords: Agrochemical industry Multistream efuents Air stripper BTSSBR Filtrationadsorption process

1. Introduction Agrochemical industries play an important role in Indian economy, and in satisfying the food needs of 1.21 billion populations. India is the fourth largest producer of agrochemicals after the United States, Japan and China (FICCI, 2010). Agrochemicals are bioactive agents used for controlling pests and insects to enhance crop production (Kenawy and Macromol, 1998), and are classied as pesticides, insecticides, herbicides and fungicides. In India, con Corresponding author. Tel.: +91 712 2249763; fax: +91 712 2249900.
E-mail addresses: p_manekar@neeri.res.in, pravinpmanekar@rediffmail.com (P. Manekar). 0960-8524/$ - see front matter 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.biortech.2013.08.145

sumption of insecticides is around 67% as compared to 33% globally. Agrochemical industries consume enormous water for producing the pesticides, insecticides, herbicides and fungicides and generate multistream complex efuents. Discharging of untreated or partially treated agrochemical efuent render adverse effects on receiving water bodies (Delorenzo et al., 2001). Chemicals present in agrochemical efuent are often toxic to aquatic life. Technologies such as multiple effect evaporation (MEE), mechanical vapor recompression and spray dryers (Vishnu et al., 2008; Narmine et al., 2003), available for treating the high total dissolved solids (TDS) and high chemical oxygen demand (COD) efuent are energy intensive. Condensates obtained through these

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processes typically low in TDS and high in COD, and are heavily loaded with toxic ammonia. Steam or air stripper is commonly used to effectively remove ammonia from wastewater due to its simplicity of operation and cost effectiveness (Minhalma and Pinho, 2004; Maranon et al., 2008b). Pretreatment technologies for the low TDS and high COD efuent comprise physico-chemical and biological processes (Minhalma and Pinho, 2004). However, unlike chemical treatment biological process does not produce a huge quantity of sludge and thus are more environmentally friendly (Eckenfelder and Grau, 1992). Biological processes such as activated sludge process (ASP), sequential batch reactors (SBR), anaerobicaerobic (A/O) biolm reactors, moving bed membrane bioreactor, packed-bed biolmreactor and pre-denitrication can effectively remove carbonaceous and nitrogenous pollutants (Kim et al., 2009; Yang and Yang, 2011; Chang et al., 2012; Karkare and Murthy, 2012; SandovalCarrasco et al., 2013). Recently many new technologies based on anaerobic ammonium oxidation process (ANAMMOX) have come up such as SHARONANAMMOX, CANON, OLAND, and DEAMOX etc. (Bagchi et al., 2012). However, these technologies are applicable for wastewater with low C:N ratio. Various researchers have also tested the possibility of advanced oxidation process such as wet air oxidation, catalytic wet air oxidation, ozonation and microwave radiation for treatment of complex industrial wastewater (Yang et al., 2007; Lin et al., 2009). Agrochemical efuents are typically characterized with high concentrations of COD and ammonia. Treatment of wastewater with high concentrations of COD and ammonia requires stepby-step removal of carbon and nitrogen through COD oxidation, nitrication and denitrication. Such treatment scheme is not only complicated, but also cost intensive. Single-stage process such as ASP with extended aeration and SBR process are often used as an alternative to nitrication and denitrication process. The SBR has been successfully employed in the treatment of both municipal sewage and industrial efuent (Mace and Mata-Alvarez, 2002). It is simple in process engineering, design and requires less foot print (Vazquez et al., 2006). This technology is a cyclic batch process operated in a sequence of ll, react, settle and decant for effective removal of pollutants (Akin and Ugurlu, 2005) and best suitable for accommodating multiple microbial reaction in a single reactor. However, carbon and nitrogen removal can suffer from disagreement of demand and supply of substrates between two metabolically different groups of microorganism namely the heterotrophs that oxidized carbonaceous pollutant and the autotrophs that oxidized ammonia. This disagreement coupled with competition between various groups of autotrophic and heterotrophic microorganisms in the same space for nutrients and oxygen often leads to failure (Kim et al., 2013a). The competition become more intense when complex industrial efuent are treated such as efuent from steel industry, coal carbonization, cove oven industry and municipal leachates, etc. (Marttinen et al., 2002; Pi et al., 2009; Biswas et al., 2010; Manekar et al., 2011b). To overcome the incompatibility between heterotrophic and autotrophic bacteria in a single stage reactor, two-stages processes are often advocated for treating high strength efuent (Luo et al., 2011; Kim et al., 2013b). Agrochemical industry also generates wastewater with high concentration of COD and ammonia. To the best of our knowledge, no studies have been reported in literature on biological treatment of agrochemical efuent. This paper described the rst ever report on two-stages bio-oxidation of agrochemical efuent for carbon and nitrogen removal. Additionally, dwindling availability and increasing demand of fresh water have put industries under intense pressure to comply with the zero liquid efuent discharge (ZLD) norms for recycling the treated water. In absence of adequate treatment processes,

enhanced membrane fouling, and increased the membrane pressure becomes the bottleneck for producing good quality recycled water (Manekar et al., 2011a). The objective of the present study is to develop the process for treating the agrochemical efuent by overcoming the microbial imbalance between the demand and supply of substrate in autotrophic and heterotrophic bacteria, improving the process stability and nally achieving effective treatment with minimum chemical consumption meeting the criteria of membrane feed water quality (MFWQ) and Inland Surface Waters standards of India. A well bioengineered two-stages bio-oxidation processes integrated with physico-chemical could be a viable pretreatment process for treating and generating MFWQ from agrochemical efuent. Thus, the work aimed at the investigation of the bioengineered two-stages SBR for treatment of agrochemical efuent. Further to this, applicability of the physico-chemical techniques such as air stripping and ltrationadsorption were also explored at the primary and tertiary level. Additionally, herein we also report the design aspect of the BTSSBR process for setting up a full scale efuent treatment facility. 2. Methods 2.1. Study area The agrochemical industry is located in the southern part of India. The production capacity of the industry is 12.5 tonnes per day. The production unit comprises four process blocks designated IIV, and produces a comprehensive range of pesticides, technical, formulations and custom manufactured ne chemicals. Multiple streams of agrochemical efuents are generated during the manufacturing process. 2.2. Quantify of process efuent Segregation of process efuents is an important step for isolating specic pollutant and treating them in a techno-economical way. The complex process efuents generated from the four manufacturing units (namely block IIV) were segregated into three main streams, and designated as stream AC. The stream A was generated after product separation; ejector condensates from all the process blocks were channelized in the stream B. Stream C, highly organic in nature was left over solvent separation. The process efuent generated from the various blocks and their segregation is shown schematically in Fig. 1. The quantum of streams A, B and C generated were 250, 300 and 30 m3 d1, respectively. Stream C was directly incinerated and hence was not considered in the present study. 2.3. Existing treatment facility Flow scheme of the existing treatment facility is presented in Fig. 1. Stream A was treated in evaporative system, and condensate obtained was stripped in an air stripper. The stripped efuent was further combined with stream B before feeding to a single-stage aerobic bioreactor. The sludge from biological process and concentrate from the evaporator system were dried separately on sludge drying beds, and nally, the dried sludge and concentrate were disposed off to a treatment storage and disposal facility. 2.4. Efuent sampling Hourly samples were collected in polypropylene bottles and composited for 24 h at different stages of the efuent treatment plant (ETP). The parameters like pH, temperature, dissolved oxygen (DO) concentration and TDS were immediately analyzed at the site

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Process blocks (I,II,III,&IV)

Product separation & mother liquor

Ejector condensate

Solvent recovery & product separation

Stream A

Stream B

Stream C

(ratio of efuent from blocks I/II, III and IV 3:3:4), and the pH of the composite efuent was adjusted to specic values (9.5, 10, 11 and 11.5) using 1 N NaOH solution. The stripping experiments were conducted by feeding composite efuent from the top using a peristaltic pump and to facilitate the transfer of ammonia from the efuent to gas phase, counter current compressed air was injected from the bottom for a batch period of 2 h. During the batch operation, stripped efuent was continuous recycled. The studies were carried out on four sets of pH (9.5, 10, 11 and 11.5) and air to efuent ratio (925, 1100, 1333, and 1525) by varying the feed ammonia concentration from 738 to 1370 mg l1 for each set.

Multiple effects evaporators

Condensate

Ammonia stripper

Rotary kiln incinerator

Flue gas

Forced circulation evaporator

Bio-oxidation

Spray Dryer

To rotary kiln incinerator

Membrane System Rejects to

MEE

Dired salt

Permeat Cooling tower makeup

Fig. 1. Flow scheme of multistream efuent generation and treatment of agrochemical industry.

using a digital multi-meter. The composite samples were also analyzed for selected parameters relevant to efuent treatment and discharge standards. The parameters such as suspended solid (SS), chemical oxygen demand (COD), biochemical oxygen demand (BOD), phenol, and ammonia nitrogen (NH3-N) were analyzed according to the standard protocols as referred in the Standard Methods for the Examination of Water and Wastewater (APHA, 2005). 2.5. Experimental setup Lab scale studies on agrochemical efuent were carried out in a custom made experimental setup (Fig. 2). Brief descriptions of the experimental setup are given below. 2.5.1. Air stripper A vertical glass column (5 cm diameter), uniformly packed with pebbles of an average size (1.5 0.75 cm2) was used as a stripping medium for ammonia stripping. Effective height of the stripping bed was 32 cm. Three portions of condensates from the evaporative system was mixed with one portion of composite stream B

2.5.2. BTSSBR Ammonia stripped efuent was treated in a bench scale BTSSBR as shown in Fig. 2. The BTSSBR consists of two cubical acrylic tanks of size (30 30 30 cm3). The rst-stage SBR (FSSBR) was inoculated with the biomass collected from the existing ETP of the agrochemicals industry. Biomass to be inoculated in second stage SBR (SSSBR) was obtained from an industrial nitrication unit and acclimatized for 30 days with domestic sewage. The FSSBR was fed with stripped efuent (pH 7.2) at different hydraulic retention times (HRTs) in an extended aeration mode. The bioengineered rst and second stage SBRs were operated in a cyclic batch mode having a time schedule as follows: 4 h-lling, 18 h-lling and aeration (both oxic); 2 h-settling, 4 h-decanting (both anoxic). The BTSSBR system was optimized by operating reactors at different HTRs (14 d). The HRT was maintained at a desired value by controlling the ow rate of feed using a peristaltic pump. In the SSSBR, the pH was maintained around 6.9 0.25 using dilute phosphoric acid. An alkalinity to NH3-N ratio of 5 was maintained by adding sodium bicarbonate. It also served as a carbon source for autotrophic bacteria. Air was supplied articially so as to maintain a DO concentration 2.5 mg l1 and to ensure proper contact of substrates and microorganisms during ll and aeration mode. The bio-oxidized efuent from the BTSSBR was subsequently subjected to a combined ltrationadsorption process.

2.5.3. Combined ltrationadsorption process 2.5.3.1. Sand ltration. First, the bio-oxidized efuent was passed vertically downwards through a packed bed (4 cm diameter, 3 cm in height) of sand and gravel at different ow rates (711 m3 m2 h1). The height of the gravel (particle size 12 cm) bed at the bottom was 5 cm. The middle portion of the column (18 cm) was lled up with 0.81.2 mm, whereas the top

To tertiary treatment Stripped effluent P C FSSBR SS D SW FSSBR effluent P D SSSB SS SW

C Feed Air

Air stripper

Legends
FSSBR SSSBR C P : : : : First stage SBR Second stage SBR Compressor Pump DA SSZ SW : : : Diffused aeration Sludge settling zone Sludge withdrawal

Fig. 2. Laboratory experimental setup of air stripper and two-stage SBRs.

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5 cm was packed with sand of particle size less than 0.8 mm. The uniformity coefcient of sand (D60/D20) was 1.45. 2.5.3.2. Activated carbon column. After effective trapping of suspended solids in the sand lter bed, the ltrate efuent was fed into the top of a packed bed (4 cm 32 cm) of granular activated carbon (GAC) using a peristaltic pump. The column ow rate was varied from 7 to 9 m3 m2 d1. GAC characteristics were as follows: Sieve size 4 + 8 BSS; bulk density 0.55 gc c1; hardness 96. The residual organic were adsorbed, and hence got removed as the efuent moved downward through the GAC bed. 3. Results and discussion 3.1. Physico-chemical characterization of efuents A detailed physico-chemical characterization of streams A and B, generated from the different process blocks IIV was carried out, and the results are summarized in Table 1. TDS and COD concentrations of stream A (from process blocks IIV) were very high in the range 160,000253,000 and 56,28084,000 mg l1, respectively and hence stream A was characterized as high TDS and high COD efuent. The COD concentration of stream B (from process blocks IIV) was 57 times more than its TDS concentration. Therefore, it was characterized as low TDS and high COD efuent. Additionally, ammonia and SS concentrations in stream A were much higher than stream B. In totality, all the stream from agrochemical efuent was characterized high strength efuent containing high concentration of organic, inorganics and ammonia. The process efuents were found to be free from pesticides, herbicides, fungicides and insecticides. 3.2. Performance evaluation of existing treatment facility The ETP of the agrochemical industry was equipped with multiple effect evaporators (MEE) and force circulation evaporation (FCE), air stripper and single-stage biological oxidation unit. The biological unit was operated on the principle of a single-stage carbonnitrogen removal in a sequential batch reactor (SBR). The layout of the existing treatment scheme is presented in Fig. 1. The performance of the ETP under the existing operating condition was assessed, and the physico-chemical characteristics range of feed, concentrate and condensate for MEE and FCE is presented in Table 2. The TDS concentration of MEE concentrate was 58 73%, and further concentrated in FCE to 9092%. The MEE-feed was over loaded with high TDS concentration (16.025.3%) as against 10% design, resulting in high TDS and ammonia concentrations (50405444 and 22602870 mg l1, respectively) in condensate. This in turn adversely affected the performance of the

downstream air stripper. The inuent and efuent characteristics from air stripper are presented in Table 3. The stripping efciency (%), as evident from Table 3 was extremely poor. Ammonia laden efuent from the air stripper was biologically treated in a single-stage SBR operated in a cyclic batch mode with a cyclic period 4 h-lling (oxic); 20 h-lling and mixing and aeration (oxic); 2 h-settling (anoxic); 2 h-decanting (anoxic). Diffused aeration was used for mixing and aerating the content in SBR tank. The performance of the single-stage SBR and treated efuent quality as per the stipulated discharge norms into Inland Surface Waters and required membrane feed water quality for reverse osmosis are summarized in Table 4. The inuent to SBR was high in ammonia concentration (305385 mg l1). The dissolved oxygen (DO) concentration during the ll and the aeration period was found to be less than 1 mg l1. The mixed liquor volatile suspended solid (MLVSS) and mixed liquor suspended solid (MLSS) concentrations were 14522000 and 21002500 mg l1, respectively. The desirable DO concentration in the tank during aeration period for nitrication is 2.5 mg l1. Similarly biomass concentration as reected by MLSS should be more than 3000 mg l1 for effective bio-oxidation (Metcalf and Eddy, 2003). 3.3. Bench scale treatability studies Presence of high concentration of ammonia in the stripped efuent and inadequate removal of COD and NH3 in the existing single-stage SBR demanded further improvement in the treatment process so as to meet a MFWQ. 3.3.1. Air stripper Inadequate air to efuent ratio (430) in the existing air stripper resulted in high concentrations of ammonia (14281834 mg1) in stripped efuent. High concentrations of NH3 have toxic impact on the biological process. To carry out a bench scale experiment, stream B was rst pre-composited from process P- I and II efuent, P-III process efuent and P-IV process efuent in a ratio of 3:3:4, and further combined with MEE condensate in a ratio of 3:1 before feeding to the air stripper. The characteristic of air-stripper feed was as follows: pH: 9.29.7; TDS: 14602700 mg l1; COD: 28896320 mg l1; BOD: 20004833 mg l1 and ammonia 738 1240 mg l1. The air stripper was operated in a batch mode by varying the feed ammonia concentration for four sets of pH and air to efuent ratio. During each set, the ammonia removal was observed to increase with increased in feed pH from 9.5 to 11.5 and air to efuent ratio (8001333) (Fig. 3). Among four sets of experiments conducted with the combined efuent, the highest and the lowest ammonia removal efciency achieved was 92% at pH 11.5 and air to efuent ratio 1333 and 59% at pH 9.5 and air to efuent ratio 800, respectively. Volatile COD removal was 25% at pH 9.5 and air to efuent ratio 800 to 45% at pH 11.5 and air to efuent ratio 1333. The maximum ammonia removal efciency achieved at an optimum pH of 11.5 and air to efuent ratio of 1333 with an air ow rate 1.2 l s1. Previously, Pi et al. (2009) and Marttinen et al. (2002) has reported similar results, but with much higher air to efuent ratio (3500). Supplying air ow rate of 1.4 l s1, Quan et al. (2009) achieved a little higher ammonia removal efciency (97%). In our case, the ammonia concentration in the stripped efuent was less than 200 mg l1. Thus, the optimized air stripping process effectively stripped ammonia more than 90% from the combined process efuent, and helped to reduce the toxic load on the downstream bio-oxidation process. However, further treatment of stripped efuent was necessary to remove dissolved carbonaceous and nitrogenous substrates.

Table 1 Physico-chemical characteristics (range) of stream A and B. Parameters Multistream efuent Stream A Process block IIV pH Alkalinity SS TDS COD BOD Ammonia Phenols 10.411.3 530014,730 16506110 160,000253,000 56,28084,000 21143220 I & II 10.611.3 4161270 268 12902020 712013,760 40008780 280616 215 Stream B III 9.110.3 1841480 24 3482370 33606640 20002800 380716 10119 IV 8.18.6 1501860 274 14202120 13602880 24003166 11.256 10114

All values are expressed in mg l1, except pH.

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Table 2 Physico-chemical characteristics (range) of feed, condensate, concentrate for MEE and FCE. Parameters Feed MEE Condensate pH Alkalinity SS COD Ammonia TDS Chloride Sulphate Sodium Potassium 10.411.3 530014730 16506110 56,28084,000 21143220 160,000253,000 28,03139,760 938525,385 22,72438,029 190309 10.310.8 10201620 212 50405444 22602870 496989 215238 BDL-17 148153 24 Concentrate 10.711.1 12,14012,800 11,180133,490 162,700205,800 701134 582,000737,000 157,673158,330 40,61567,250 121,982135,194 488541 FCE Condensate 11.111.2 10,80019,100 96118 67,200117,600 14002604 43,900144,000 773934,037 55585762 769824,890 37100 Concentrate 10.710.9 64,70082,700 23,200225,680 268,800428,400 126196 622,000820,000 168,674173,176 54,15488,476 135,632155,030 620678

All values are expressed in mg l1 except pH; MEE multiple effects evaporator; FCE forced circulation evaporation.

Table 3 Performance of air stripper. Parameters Inlet Outlet after 0.5 h pH COD TDS Ammonia Phenol 9.49.7 56006880 30603250 14281834 100121 9.49.7 48705440 29203020 14561540 100127 1h 9.39.7 49205458 29403030 14981568 100124 1.5 h 9.49.7 47654900 28303000 13721400 100125 2h 9.49.7 51205312 29453070 14501596 100122 Ammonia removal (%) 0.5 h NR-16 1h NR-14 1.5 h 4-24 2h NR-13

All values are expressed in mg l1, except pH. NR no renoval.

Table 4 Performance of existing SBR vis--vis Inland Surface Waters discharge standards. Parameters SBR Inlet pH SS COD BOD Phenol Total NH3-N 10.010.7 100200 17506400 8922995 2.220.9 305385 Outlet 6.78.1 4170 5501502 250505 BDL-2.0 172400 5.59.0 100 250 30 5 50 6.4 100 250350 50150 5 50 Discharge standardsa Inlet feed water quality for RO

All values are expressed in mg l1, except pH; BDL below dectable limit; RO: reverse osmosis. a Indian standards for discharge into Inland Surface Waters.

3.3.2. First-stage SBR (FSSBR) In the existing treatment facility, 5965% SS, 7283% BOD and 6877% COD removals were achieved in the single-stage SBR. Ammonia removal was not taking place in the existing facility even after operating the reactor at an extremely high HRT of 24 days. The treated water quality from the existing SBR neither conformed to the Indian Inland Surface Waters (ISW) standard discharged nor met the MFWQ with respect to BOD, COD and ammonia concentration (Table 4). Due to the inadequate stripping of ammonia in the air stripper, ammonia laden efuent posed toxicity risks on the downstream, single-stage bio-oxidation process. This was further conrmed by low numbers of nitrifying bacteria present in the biomass (778 102 CFU ml1) in comparison to total bacterial counts (500650 107 CFU ml1). Nitrication failure due to low population of nitriers in a full-scale plant treating industrial efuent has also been reported by other workers (Kim et al., 2013b). Laboratory studies were carried out in a 24 h cyclic rst-stage bio-oxidation reactor at mixed liquor suspended solid (MLSS) concentration of 32003500 mg l1 with varying HRTs (14 days). The results from this set of the experiments are presented in Fig. 4. The removal of the major pollutant parameters such as COD and BOD at HRT 1 day was 70% and 75%, respectively. When the reactor was operated at higher HRTs, the increase in the removal of pollutants (COD and BOD) was observed. However, at HRT greater than

3 days, COD and BOD removal efciency dropped to 80% and 86%, respectively. Biological process depends on the bacterial growth/decay rate and HRT that yield desired treatment efciency. A large reactor often overrules the economically viability of the treatment. Therefore, to ensure desired efciency yield in a costeffective way, optimization of HRT is of prime importance to ensure maximum efciency yield for the FSSBR. The highest removal of carbonaceous substrate was obtained at 3 d (72 h) HRT with more than 90% removal efciency. Maranon et al. (2008b) reported a very similar COD removal efciency at HRT of 115 h in a single stage SBR for treatment coke efuent. The treated efuent characteristics from the FSSBR were as follows: COD: 400 mg l1; BOD 250 mg l1; ammonia nitrogen: 200 mg l1. The results obtained were comparatively better than the existing full-scale SBR. This was mainly due to effective stripping of ammonia in stripper that reduced the toxicity and enhanced the degradation of carbonaceous substrate through heterotrophic bacteria in FSSBR. However, treated efuent did not meet the Indian ISW discharge standards. Therefore, further treatment was necessary to meet the regulatory norms. 3.3.3. SSSBR Presence of biodegradable COD in ammonia laden efuent directly promoted growth of heterotrophic bacteria. Also,

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Inlet ammonia

Outlet ammonia

Average ammonia Conc. mgl-1x 100

Per cent removal

14 12 10 8 6 4 2 0 1 2 3 4 No. of run 5

Average ammonia Conc. mgl-1x 100

75 70 Per cent removal 65 60 55 50

14 12 10 8 6 4 2 0 1 2 3 4 No. of run 5

75 70 65 60 55 50 Per cent removal

(a) pH:9.5; Air to effluent ratio:800 Average ammonia Conc. mgl-1x 100 pH andAmmonia concentration, Average ammonia Conc. mgl-1mg/l x 100

(b) pH:10; air to effluent ratio:925

Inlet ammonia Outlet ammonia Per cent removal pH

14 12 10 8 6 4 2 0 3 4 5 No. of run (c) pH:11; Air to effluent ratio:1100 1 2

85 80 Per cent removal 75 70 65 60

14 12 12 10 10 8 8 6 6 4 4 2 2 0 0

95 95 90 90 85 85 80 80 75 75 70

Per cent removal Percent removal

3 4 5 3 4 5 No. of run No. of run (d) pH:11.5; Air to effluent ratio;1333

1 1

2 2

Fig. 3. Effect of pH and air to efuent ratio on ammonia removal.

Effluent COD65 Effluent Ammonia40 COD removal

700 600
-1

Effluent BOD20 BOD removal

100

25 days operation for each set of HRT

90 500
Per cent removal

400 300 200

80

70

60 100 0 1 2
HRT, days

50 3 4

Fig. 4. Performance of rst-stage bio-oxidation process at different hydraulic retention time.

considering the fact that the growth rate of heterotrophic bacteria is higher than autotrophic bacteria, nitrication failure due to weeding effect of heterotrophic bacteria is not unlikely. In single stage process, heterotrophic bacteria out compete the autotrophic bacteria for space, oxygen demand and other nutrients, resulting in repression of nitrication. Once the repressed, nitrifying bacteria take a long time to recover (Kim et al., 2013b). For effective nitrication, it was essential to remove the major portion of organic matter from the efuent (Metcalf and Eddy, 2003). Thus, the FSSBR

oxidized around 90% of COD at HRT 3 d leaving behind around 200 mg l1 of ammonia and 400 mg l1 of residual COD. The SSSBR was targeted for nitrication of FSSBR efuent. Therefore, to develop nitrifying activity in SSSBR biomass from a full-scale nitrifying reactor was acclimatized with FSSBR efuent. After acclimatization, which lasted for around 3 months it was found 18% and 7% of biomass was composed of ammonia oxidizing bacteria (AOB) and nitrite oxidizing bacteria (NOB) with bacterial count of 5 27 107 and 210 107 CFU ml1, respectively. The nitrication performance of SSSBR was observed at different HRTs. Fig. 5 presents the average performance of the SSSBR against varying HRTs of 14 d. At lower HRT, the removal efciency of the ammonia was inefcient. Removal efciency increased with increase in HRT up to 3 d. However, further increase in HRT resulted in decrease in removal of ammonia. Peak 97% removal efciency of ammonia was obtained at 3 d HRT in an extended aeration mode. The time needed for nitrifying ammonia in the present study was accordance to removal of carbonaceous and nitrogenous substrates in wastewater by a mixed microbial population (Metcalf and Eddy, 2003) which takes approximately 58 d after the start period of organics matter degradation. Many researchers have reported a minimum of 2.58 d for more than 70% nitrication efciency (Amor et al., 2005; Maranon et al., 2008a; Biswas et al., 2010; Manekar et al., 2011b). At 3 d optimal HRT, the SSSBR treated efuent had the following characteristics COD 6 110 mg l1, BOD 6 50 mg l1, ammonia 6 10 mg l1, nitrite: BDL and nitrate 6 7 mg l1. Thus, along with ammonia removal, the COD of 72.5% and BOD of 80% removals were also observed in SSSBR. Recent studies have revealed that Nitrosomonas sp., can utilize some low molecular weight organic compound and VOCs (Arp et al., 2007). Similarly, the heterotrophic sp., are commonly found in nitrifying system when operated at an extended aeration mode and various communities co-exist in a manner similar to the natural environment (Biswas et al., 2010; Kalyuzhnyi et al., 2010). Also, some aerobic

Effluent average concentration, mgl

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Effluent Ammonia4 Nitrite: BDL

35 25 days operation for each set of HRT
-1

Nitrate1 Ammonia removal

100

70
Five sets for each filtration rate

60

Per cent removal

50 40 30 20 10 0 7 8 9 10 11 12
COD removal (Sand) BOD removal (Sand) BOD removal (Activated carbon) COD removal (Activated carbon)

30 90 25 Per cent removal

Effluent average concentration, mgl

20 80 15

10 70 5

Filtration rate m -3m-2d-1

Fig. 6. Effect of ltration rate on removal of SS, BOD and COD (sand and activated carbon media).

0 1 2 HRT, days 3 4

60

Fig. 5. Performance of second-stage bio-oxidation process for nitrication at different hydraulic retention time.

heterotrophic bacteria like Bacillus sp., Pseudomonas stutzeri, Pseudomonas aernginosa, Propinibacteriun theonii, Paracoccus denitricans, etc., that are commonly found in a nitrication unit are capable of reducing the both COD and ammonia (Bagchi et al., 2012). Results of two-stages bio-oxidation process demonstrated that carbon and ammonia served as the primary substrate to the microorganisms in FSSSBR and SSSBR, respectively. Heterotrophic bacteria oxidized the carbonaceous substrate to more than 90% efciency. Autotrophic bacteria in the SSSBR effectively oxidized ammonia concentration to 97% and thus, improved the stability of nitrication process. The bioengineer stage separation provided separate environmental condition for optimum activities of heterotrophic and autotrophic bacteria (Vazquez et al., 2006; Biswas et al., 2010; Manekar et al., 2011b). Bioengineering of the single-stage biological process into a two-stage fends off the competition between heterotrophic and autotrophic bacteria, improves the process stability for substrate sensitivity through active interaction of substrates and renders the optimum environmental conditions to microbes for effective oxidation of carbonaceous and nitrogenous substrates. Thus, effective carbonnitrogen removal in the BTSSBR system was achieved at an optimal HRT of 6 d. The nal efuent from the BTSSBR met the discharge standards for ISW, with respect to all parameters except BOD. 3.3.4. Tertiary treatment To achieve MFWQ the efuent from BTSSBR was treated through tertiary treatment. The sand lter was fed with BTSSBR claried efuent at different ow rates (812 m3 m2 h1 for 5 runs). The effect of ltration rates on SS, COD and BOD removal is presented in Fig. 6. The optimum COD and BOD removals were 40% and 45%, respectively at a ltration rate of 10 m3 m2 h1. The minimum removal of COD and BOD (25% and 30%, respectively) was obtained at a higher ltration rate of 12 m3 m2 h1. The SS removal efciency for all the runs was 100%. The optimum removal efciencies of SS, COD and BOD (100%, 40% and 45%, respectively) as obtained in this study at a ltration rate of 10 m3 m2 h1 were better than the optimal removal of these parameters achieved by sand ltration of a post-secondary process efuent at a

two times slower ltration rate of 5 m3 m2 h1 (Hamoda et al., 2004). Sand-ltered efuent was passed through an activated carbon column at different ow rates (711 m3 m2 h1 for 5 runs). The effect of ltration on the BOD and COD removal efciency is presented in Fig. 6. The optimum COD and BOD removal (44% and 55%, respectively) was obtained at a ltration rate of 9 m3 m2 h1. The physico-chemical characteristics of GAC treated efuent were as follows: pH 6.57.5, TDS 6 2700 mg l1, COD 6 50 mg l1, BOD 6 15 mg l1 and ammonia 6 10 mg l1. The combined ltrationadsorption process was found to consistently produce membrane feed-quality water from the BTSSBR efuent. 3.4. Design of full-scale ETP Partial removal of high organic content and ammonia nitrogen from complex agrochemical efuent through the single-stage bio-oxidation process leads to serious deleterious effects on the receiving aquatic bodies. Operational parameters of the BTSSBR and combined ltrationadsorption process optimized in bench scale models were further elaborated to design a technically viable treatment scheme for agrochemical efuent having low TDS and high COD content. The main objective of the BTSSBR followed by combined ltrationadsorption process was to design and implement full-scale ETP to meet the discharge norms for ISW as well as to produce MFQW for intended reuse. The proposed schematics of the ETP along with the design characteristics of various unit operations and processes are presented in Fig. 6a, and the details are presented in Table 5. The equalization basin volume for a detention time of 1 day required before air stripping is calculated using the following equation:

Volume Flow Detention time

wherein volume is expressed in m3, ow in m3 d1 and detention time in h. The power required to keep the entire efuent in suspension was 12 kW. The full-scale BTSSBR was designed to operate in a cyclic batch mode with a time schedule for FSSBR: 4 h-lling, 18 h-lling and aeration (both oxic), 2 h-settling (anoxic), 4h-decanting (anoxic) and SSSBR: 4 h-lling, 20 h-lling and aeration (both oxi); 2 h-settling, 2 h-decanting (both anoxic). The yield coefcient (Y) of the BTSSBR cycle was 0.4 g g1, while the endogenous respiration coefcient (kd) was: 0.035 d1. The full-scale BTSSBR was designed with 6 days total HRT and 3 days at each stage, operating in an extended aeration mode. The loading rates for FSSBR and SSSBR were 0.750 and 0.083 kg BOD m3 d1, respectively. The oxygen demand for the

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Flow: 600m3d pH: 11.5 -1 TDS:2800mgl -1 COD: 5290 mgl -1 PNH3: 1395 mgl

-1

Flow: 600m3d pH: 7.0-7.3 -1 TDS:2700mgl -1 COD: 3000 m l -1 BOD: 2500 mgl -1 NH3: 200 mgl

-1

pH: 6.8 -7.3 -1 TDS:2700mgl -1 COD: 700mgl -1 BOD: 250 mgl -1 NH3: 200 mgl

pH: 6.5-7.5 -1 TDS:2700mgl -1 COD: 250mg l -1 BOD: 100 mg l -1 NH3: 50 mg l

pH: 6.5-7.5 -1 TDS:2700mgl -1 COD: 100mg l -1 BOD: 30 mg l -1 NH3: 50 mg l

B1 B P
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MEE Condensate Process from Blocks Effluent I-IV

Equalization basin

Air Stripper

CT

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CT
P

SBR stage-I P

SBR stage-II

PSF

CT

ACC Membrane separation process

Legend
o P A B& B1 C SBR PSF ACC MEE TSDF SDBs Diffused aeration Pump Mixer Sodium hydroxide tanks Orthophosphoric acid tanks Sodium bicarbonate Sequential batch reactor Pressure sand filter Activated carbon column Multiple effects evaporator Treatment storage and disposal facility Sludge drying beds.

Sludge collection tank

P P

SDBs Gravity thickener

Centrifuge TSDF

Supernatant

Fig. 6a. Schematics of proposed treatment process.

Table 5 Details of proposed efuent treatment plant. Unit description Equalization tank SBR-I SBR-II Collection tank Pressure sand lter Collection tank Activated carbon tank Treated efuent collection tank Gravity thickener Quantity One Two Two One One One One One One Dimension (L B D) m 12.25 12.25 4 (+0.5 FB) 14.2 14.2 5 (+0.5 FB) 13.5 13.5 5 (+0.5 FB) 2 2 1.25 (+0.3 FB) 2 Dia 3 (+0.5 FB) 4.1 4.1 3 (+0.5 FB) 2.1 Dia 5 height 14.2 14.2 3 (+0.5 FB) 3.9 Dia 3 H (+0.5 FB)

Acknowledgement The authors acknowledge Dr. S.R. Wate, Director, CSIR-National Environmental Engineering Research Institute for providing valuable suggestions during the course of study. References
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L length; B breath; D depth; FB free board.

BTSSBR was determined as described previously (Manekar et al., 2011b). The oxygen demand for FSSBR and SSSBR was 2220 and 1 1 565 kg d O 2 , respectively. The power requirement to meet the oxygen demand of BTSSBR was 150 kW. The sand ltration and activated carbon column were designed for the optimized ltration rate 10 and 9 m3 m2 h1, respectively. The contact time in the adsorption column was 30 min.

4. Conclusions Agrochemical efuent is composed of high concentration of ammonianitrogen, organic and inorganic matter. This efuent poses a serious threat on bio-oxidation and aquatic lives, and hence essentially requires an effective BTSSBR process. Ammonia is stripped in air stripper. Carbon management in the rst-stage and nitrogen in the SSSBR fends off microbial competition and improves the process stability through active interaction of substrates and bacteria that a single-stage process often suffers. The study demonstrates that the process comprising air stripper, bioengineered two-stages sequential batch reactor and ltration adsorption is a techno-economically viable scheme for treating agrochemical efuent to environmentally acceptable form.

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