Abstract
The magnitude of pH changes in polishing ponds can be predicted by simple stoichiometric rules if the extent of processes affecting this parameter is known. Thus, the objective of this article was to develop a model that predicts pH variation and ammonia desorption in polishing ponds in sequential batches, depending on the rates of processes that affect pH in ponds and to evaluate the influence of temperature and depth on these processes. As the temperature conditions change during the year, for model validation, tests were carried out under two medium temperature conditions (hot period and cold period) and four lakes with depths between 0.2 and 1.0 m. The proposed model is validated by the good correspondence between the simulated and experimentally obtained values for the two temperature conditions and for both periods. For the hot period, the model excelled, presenting a high linear correlation, always with R 2 above 0.90 for all ponds. For the cold period, the lowest R 2 obtained was 0.74 for the four lakes. Thus, the proposed model is suitable to describe the pH variation and ammonia desorption in polishing ponds in sequential batches, at all analyzed depths and under both temperature conditions.
HIGHLIGHTS
A predictive model of pH variation and ammonia removal for sequential batch polishing ponds was developed.
The model showed a high correlation between simulated and experimental values. Finding out how in SBPP the removal of ammonia takes place through volatilization.
The predictive model can be used in SBPP for various conditions (temperature, depth, sewage characteristics) to obtain the retention time required for ammonia removal with good accuracy.
The results indicate that SBPP requires a much smaller area than WSP, still showing ammonia removal.
INTRODUCTION
According to Sbahi et al. (2021), the best criteria for choosing an effluent treatment system are high efficiency and low cost. UASB reactors (upflow anaerobic sludge blanket) have efficient organic material removal and a relatively low cost, and are widely used in many countries with hot climates as the first stage of effluent treatment (van Haandel & Lettinga 1994; von Sperling 2015). In Brazil, using a UASB reactor necessarily requires effluent post-treatment units to meet current release standards (van Haandel et al. 2006). This is because UASB reactors do not remove nutrients, pathogenic organisms, and surfactants sufficiently, therefore a post-treatment step is necessary not only for the additional polishing of the effluent in terms of organic matter concentrations (van Haandel et al. 2006; Walia et al. 2020).
Khan et al. (2011) report that there is a wide variety of post-treatment configurations that are based on combinations with UASB reactors, one of them being polishing ponds (PPs). PPs are shallow and designed specifically to improve UASB effluents. Due to the relatively low oxygen demand in PPs and the high photosynthesis rate in the transparent UASB, effluent dissolved oxygen tends to build up, so that PPs can be operated as flow through units or in sequential batch mode. PPs constitute one of the most attractive alternatives for disinfecting effluents from UASB reactors, because complete treatment can be achieved in a much shorter time than in conventional waste stabilization ponds (WSPs). In addition. PPs present adequate conditions for nutrient and pathogen removal (Cavalcanti 2003). PPs are systems with low operating costs, as they do not need energy input other than solar energy and do not require chemical product applications (Santos & van Haandel 2021).
According to van Haandel & Marais (1999), the release of large amounts of dissolved nutrients into water bodies tends to cause an exacerbated growth of aquatic life. Thus, to maintain the quality of water bodies within their legal classification, the quality of effluents released must be controlled. In most countries, nitrogen levels in effluent from wastewater treatment plants are regulated to mitigate the possible harmful effects of nitrogen discharge into water bodies (Park et al. 2015). Thus, nitrogen needs to be removed before releasing wastewater into receiving bodies.
In PP, ammonia volatilization is reported as the main mechanism of ammoniacal nitrogen removal (Alves et al. 2011; Leite et al. 2011; Santos & van Haandel 2021). Morais et al. (2021) showed that ammonia volatilization is a first order process regarding the dissolved NH3 concentration. The ammonia nitrogen fraction can be as gas (NH3) or in ionic form (NH4+) depending heavily on pH and temperature. The ionization constant of ammonia is 9, so that at a neutral pH the undissociated form predominates and at a pH above 9. Since pH tends to increase with time, the NH3 concentration, and hence the desorption rate also increases.
The pH is not only affected by the physical and biological removal of CO2, but also by the desorption of ammonia that occurs when the pH is high. The desorption of NH3 is equivalent to the addition of a strong acid, reducing alkalinity and increasing acidity (Cavalcanti 2003).
Most studies with PPs for post treatment of UASB effluent use the flow-through regime. However, Albuquerque et al. (2021) showed that using sequential batch polishing ponds (SBPPs) is advantageous because it induces a more rapid elevation of the pH and, consequently, will accelerate the removal of nitrogen, as observed in the papers presented by Cavalcanti (2003) and Albuquerque et al. (2021). Moreover, Cavalcanti (2003) showed that bacterial decay (death) in ponds is a first-order process meaning that it is extremely advantageous to use the sequential batch rather than the flow-through regime.
According to Casagli et al. (2021), models are powerful tools for understanding, predicting and optimizing wastewater treatment systems. According to Cavalcanti et al. (2001), the magnitude of changes in pH in PPs can be predicted by simple stoichiometric rules, if the kinetics of the processes that affect this parameter are known. Thus, the objective of this article is to develop a model that predicts the variation of pH and ammonia desorption in SBPPs, depending on the rates of the processes that affect the pH in ponds and to evaluate the influence of operational conditions (notably the temperature and depth of the ponds).
MATERIAL AND METHODS
- (1)
Equalization tank (ET): used for storage and homogenization, from which the sewage was continuously pumped to the UASB reactor.
- (2)
UASB reactor: designed for a volume of 2.5 m3 and a height of 1.7 m, and to treat a flow of up to 10 m3/d of sewage.
- (3)
Storage and feeding tank (SFT): a fiber glass tank of 1 m3 for storage the UASB effluent from which it was pumped in batches to fill the PPs.
- (4)
Set of SBPPs: Consisting of four ponds made of fiberglass (PP1, PP2, PP3 and PP4), on an experimental scale, with a diameter of 0.5 m and depths of 0.2, 0.4, 0.6 and 1.0 m (volumes of 40, 80, 120 and 200 L) respectively, each pond has a register for filling and individual final effluent disposal. To keep the liquid phase homogeneous, simulating wind action, a slow mechanical stirrer with a thickness of 1 cm and a rotation speed of 6 rpm was installed in each pond. A sequential batch regime was applied, in which at each treatment cycle the treated effluent was discarded and after cleaning the ponds were fed again.
System evaluation and monitoring
The experiments were carried out in the municipality of Campina Grande-PB, located in the geographic area covered by the Brazilian semi-arid climate, where the summers are long, hot and with mostly clear skies. The winters are short, with rainfall and overcast skies. In general, the temperature varies from 20 °C to 32 °C (INMET 2020). Thus, the years can be divided into two periods: a hot period that occurs between September and May and a cold period that occurs between June and August. The experimental investigation was carried out between November 2018 and August 2019. Based on INMET data (2020), the average temperatures were calculated for both monitored periods. For the hot period, the average temperature was 25 °C and for the cold period 21 °C.
The system monitoring comprised these two temperature conditions, with sample collection time set at 9 h for both periods always carrying out daily analyses. Ammonia tests were performed, following procedures described in the Standard Methods for the Examination of Water and Wastewater (APHA, AWWA, WWF, 2012), and total alkalinity, following the Kapp method described by Buchauer (1998). A multiparameter instrument Hanna HI 98,196 pH/ORP/DO was used to record the dissolved oxygen, pH and temperature values. Table 1 shows information on batches and TDH obtained during the monitoring periods.
Pond . | Hot Period . | Cold Period . | ||
---|---|---|---|---|
N° Batches . | HRT (day) . | N° Batches . | HRT (day) . | |
PP1 | 45 | 5 | 11 | 8 |
PP2 | 23 | 10 | 5 | 16 |
PP3 | 10 | 16 | 3 | 24 |
PP4 | 8 | 30 | 3 | 30 |
Pond . | Hot Period . | Cold Period . | ||
---|---|---|---|---|
N° Batches . | HRT (day) . | N° Batches . | HRT (day) . | |
PP1 | 45 | 5 | 11 | 8 |
PP2 | 23 | 10 | 5 | 16 |
PP3 | 10 | 16 | 3 | 24 |
PP4 | 8 | 30 | 3 | 30 |
Model for pH variation and ammonia desorption in SBPP
where:
ΔAlc: Alkalinity variation (meq/L);
ΔAcd: Acidity variation (meq/L);
ΔN: Observed variation of the concentration of ammonia in the pond (mg/L);
ΔCO2des: Variation of the CO2 concentration due to desorption;
ΔDO: Net DO production (photosynthesis – respiration) (mg/L).
OPR = (dO2/dt)p = oxygen production rate in the pond (molO2.L−1d−1)
= phtosynthesis rate – oxygen consumption rate
: = biological CO2 consumption rate (molCO2.L−1d−1).
The pH variation can also be calculated from Equation (5) using changes in alkalinity and acidity. Considering that the H+ and OH− concentrations are so low that they do not influence alkalinity and acidity:
Now the basis of a model is created that can describe pH variations, alkalinity, acidity and ammonium concentrations as a function of time in the SBPP. Table 2 summarizes the equations.
Variable . | Equation . |
---|---|
DO production rate | OPR = ΔO2/Δt = −(ΔCO2 /Δt) |
CO2 desorption rate | (Δ [CO2]/Δt)d = kdc([CO2] − [CO2]s) |
NH3 desorption rate | (Δ [NH3]/Δt)d = kdn[NH3] |
Alkalinity variation | ΔAlk/Δt = −kdn[NH3] |
Acidity variation | ΔAc/Δt = −2{kdc([CO2] − [CO2]s) − 2TPO + kdn[NH3]} |
pH variation | pH1 = −log{(0,5(k1(Ac1/Alc1 − 1)/2 + ((k1(Ac1/Alc1/2)2 − k1K2)1/2)} |
CO2 variation | Δ[CO2]/Δt = –kdc([CO2] − [CO2]s) − TPO |
NH3 variation | Δ[NH3]/Δt = –kdn[NH3] |
Total N variation | ΔNtot/Δt = Ntot − kdn[NH3] |
Variable . | Equation . |
---|---|
DO production rate | OPR = ΔO2/Δt = −(ΔCO2 /Δt) |
CO2 desorption rate | (Δ [CO2]/Δt)d = kdc([CO2] − [CO2]s) |
NH3 desorption rate | (Δ [NH3]/Δt)d = kdn[NH3] |
Alkalinity variation | ΔAlk/Δt = −kdn[NH3] |
Acidity variation | ΔAc/Δt = −2{kdc([CO2] − [CO2]s) − 2TPO + kdn[NH3]} |
pH variation | pH1 = −log{(0,5(k1(Ac1/Alc1 − 1)/2 + ((k1(Ac1/Alc1/2)2 − k1K2)1/2)} |
CO2 variation | Δ[CO2]/Δt = –kdc([CO2] − [CO2]s) − TPO |
NH3 variation | Δ[NH3]/Δt = –kdn[NH3] |
Total N variation | ΔNtot/Δt = Ntot − kdn[NH3] |
In addition to the values of the constant presented in Equations (9a) and (9b), the input data of the model are the characteristics of the UASB effluent used, which are obtained experimentally. The following input data are added to the model: Total ammonia, pH and alkalinity. Acidity can be calculated from pH and alkalinity and entered as input. These values depend on the temperature and depth which are also input data. TPO is not yet defined, but can be measured experimentally as the rate of change in DO concentration (Equation (8)). According to Santos & van Haandel (2021), there seems to be no expression that links the rate of this process to operating conditions, effluent characteristics and climate, and therefore it must be determined experimentally or estimated from previous experiments in similar ponds.
As the temperature conditions change during the year, tests were carried out under two conditions of average temperature and four lakes with different depths for the validation of the model.
RESULTS AND DISCUSSION
Comparing Figures 2 and 3, it can be seen that the pH tends to rise in both periods, but due to the higher incidence of solar radiation during the hot period, this elevation is faster. For example, for PP3, on day 12 for the hot period, the average pH was 8.9, while for the cold period, the average was 8.5. However, under both conditions, the same behavior was observed for the four lakes, demonstrating that in SBPP, the pH tends to rise with the increase of retention time, which is a condition for nutrient removal. According to Cavalcanti et al. (2002), under favorable conditions (low organic load, intense solar radiation, and high temperature) the consumption of carbon dioxide caused by photosynthetic activity is sufficient to raise the pH to values in the range of 9 to 10, mainly in shallow ponds. High pH values are responsible for ammonia removal (Gonçalves et al. 2017).
When analyzing Figures 4 and 5, it appears that the HRT for ammonia removal was lower in the hot period than in the cold period. This behavior was expected and was observed by other researchers such as (Bastos et al. 2018) and (Sutherland et al. 2017).
Validation of the model to predict the pH variation and ammonium in SBPP
Figures 6 and 7 show that for different depths and temperatures, the pH increase and retention time required to achieve ammonium removal can be predicted. This prediction is confirmed according to Figures 8,910–11, which show high correlations between the estimated and experimental values. According to Assunção & von Sperling (2012) the definition of parameters that influence volatilization in polishing ponds treating effluents from anaerobic reactors and the establishment of more realistic models for this was a gap to be filled. With this work, it is verified that in SBPPs the predominant mechanism of ammonia removal is volatilization, also that this removal can be predicted for different temperatures and depths of polishing ponds.
Thus, the proposed model can now be used to evaluate the behavior of this system under a variety of conditions. For different conditions, the retention time for complete or near-complete nitrogen removal can now be predicted using the model for simulating an SBPP under specified conditions of depth, temperature and sewage characteristics.
CONCLUSIONS
Assuming that the variation of the ammonium concentration in sequencing batch polishing ponds is a first-order process that can be described by Fick's law and that the pH in these ponds can be calculated from stoichiometric calculations, a model was developed for the variation of these parameters as functions of time.
The proposed model was validated by the good correspondence of simulated values and experimentally obtained values as functions of time for a variety of operating conditions. For temperatures in the warm and cold period, it was observed that the model could predict well the pH variation and ammonia concentration for different depths. The definition of a model that could predict the removal of ammonia in PPs in the post-treatment of UASB reactor effluent was a gap to be filled.
Thus, it becomes feasible to use the predictive model to estimate the pH variation and the ammonia removal in SBPPs for different depths, temperatures, and sewage characteristics, obtaining the necessary HRT with good precision.
The experimental results also show that the required area for SBPPs is much smaller than for conventional WSPs.
ACKNOWLEDGEMENTS
The authors thank the support of ParaíbaStateResearch Foundation (FAPESQ) - Process 23038004264/2015-03 FAPESQ/CAPES, Public Notice 007/2018 (scholarship).
DATA AVAILABILITY STATEMENT
All relevant data are included in the paper or its Supplementary Information.
CONFLICT OF INTEREST
The authors declare there is no conflict.