The shortage of carbon is one of the limiting factors for the denitrification in BRCs. In order to solve the problem of unstable removal of NO3−-N and TN in the BRCs, this experiment used PB as an external carbon source to strengthen the nitrogen removal rate of the BRCs. To determine the effect of H-PBs and PBs, the investigation on the denitrification performance was conducted with three devices (BRC-A, BRC-B, and BRC-C) with different conditions. The variations of NO3−-N, NH4+-N, TN and COD were shown in Fig. 5.
3.3.1 NO3−-N, NH4+-N and TN removal rate in BRCs
Figure 5a showed the impact of H-PBs on NO3−-N removal in BRCs. NO3−-N removal rate gradually increased with the operation of the system. In the initial stage of operation, the concentration of NO3−-N in effluent was higher than that in influent, and the removal rate was in a negative state(0–10 d), but the removal rate gradually became higher in the later stage (10–20 d). There were probably several reasons accounting for this: One possible explanation is that the number of denitrifying bacteria in the device was small and the denitrifying was not obvious in the initial stage of operation. Furthermore, the system has not set up a saturated zone at the bottom of device, which cannot provide strict anoxic area for denitrifying bacteria to carry out denitrification. In addition, the removal of NO3−-N by microorganisms requires sufficient hydraulic retention time (Kavehei et al., 2021), while the permeability coefficient of FC and PC is high, thus the retention time of rainwater in the system is not enough. On the other hand, NH4+-N is converted to NO3−-N by nitrifying bacteria, resulting in accumulation of NO3−-N in the system. In addition, the filler itself contains NO3−-N, which is washed down during the influent process of the BRCs to make the effluent NO3−-N concentration even higher than the influent concentration. The NO3−-N removal rate of the BRC-C with H-PBs was always highest than that of the other two groups, followed by the BRC-B, and the lowest in the BRC-A. The removal rate of NO3−-N in the BRC-C was always positive after the 6th day. At the end of the experiment, the removal rate increased from − 20.8% in the initial stage to 58.22%, while the removal rate of the other two groups was basically negative in the first 35 d. As we all know, a combination of organic carbon source availability, NO3− availability and anaerobic soils, are required for effective denitrification (Gold et al., 2018). PBs after hydrothermal treatment continued to release carbon source and released a large amount. In BRC-C, H-PBs provided sufficient and lasting carbon source for the denitrifying bacteria in the device, so that the denitrification process could proceed normally. On the other hand, after hydrothermal treatment, the specific surface area and the internal pores of PBs increased, enhancing the NO3−-N adsorption capacity. Moreover, the addition of PBs contributed to the establishment of microbial community as denitrification is a reaction process dominated by microorganisms, in which functional microorganisms play a vital role (Wang et al., 2021). Meanwhile, the electron transfer process plays an essential role in the denitrification process, and H-PBs, as the lignocellulosic materials, can provide electron donors for denitrification (Wang et al., 2016).
Figure 5b showed the impact of H-PBs on NH4+-N removal in BRCs. The removal rates of BRCs for NH4+-N were not stable. The removal rates of the three groups of devices varied from 55–85%. At the beginning of operation of the device, the removal rate of the BRC-A was as high as 90.38%, that of the BRC-B was 85.17%, and that of the BRC-C was 82.16%, all of which were at high NH4+-N removal rates. Electrostatic adsorption is the main mechanism for removing NH4+-N (Cheng et al., 2019). Dong et al. (2020) studied the effect of ceramsite on organic wastewater treatment and found the removal rate of NH4+-N could reach to 85%. Wan et al. (2017) proposed that P and Mg on the surface of substrates could react with NH4+, and the NH4+-N adsorption capacity could be enhanced by the struvite (MgNH4PO4·6H2O) formed. It suggested that the high removal rate of NH4+-N in the earlier stage may be due to the larger specific surface area, strong adsorption effect and P, Mg contents of ceramsite. However, with the operation of the device, the removal rate of NH4+-N gradually decreased., The removal rates of BRC-A, BRC-B and BRC-C were 62.02%, 62.60% and 61.93% in 48 d, respectively, which decreased by 28.36%, 22.57% and 20.23% compared with the initial stage (0–5 d). The adsorption sites of each layer of materials gradually became saturated with the increase of the operation time of the device, leading to the desorption of NH4+-N in the process of rainfall. Since DO concentration above 1.5 mg/L is essential for nitrification (Hu et al., 2014). NH4+-N can be converted to NO3−-N by nitrification under aerobic conditions. The anoxic environment caused by the cover of PBs inhibited the growth and reproduction of nitrification bacteria, resulting in the lower NH4+-N removal rate of BRC-B and BRC-C than that of BRC-A. At the same time, the water film layer formed in the PBs during the infiltration of rainwater also greatly improved the possibility of anaerobic environment. In addition, with the extension of the system operation time, the deposition of suspended particles, the propagation of microorganisms and the development of plant roots led to the decrease of matrix porosity, system blockage and internal environment hypoxia, inhibiting the transformation of NH4+-N into NO3−-N, which was also one of the reasons for the gradual decline of NH4+-N removal rate. Also, large amounts of O2 were consumed by the increasing heterotrophic microorganisms and resulted in the inhibition of growth-rate and biological-activity of ammonifying bacteria and nitrifying bacteria as H-PBs released large amount of COD (Zou et al., 2012), Zhang et al. (2019) also found that the removal for NH4+-N of wetlands adding no biomass substrate were slightly better than other wetlands with biomass substrate. To a certain extent, this can account for the reason why the NH4+-N removal rate of BRC-C was always the lowest among three devices. The removal rate of NH4+-N decreased greatly after 35 d. In practical engineering, the soil can be loosened at 35 d to reduce the possibility of anoxic environment and improve the nitrogen removal performance of the system.
Figure 5c. showed the impact of H-PBs on TN removal in BRCs. Under the conditions of artificial simulated rainfall, the influent concentration was 12 mg/L on average. The effluent concentration of TN of the three groups (BRC-A, BRC-B, BRC-C) were 7.91 mg/L, 5.33 mg/L and 5.00 mg/L in 48 d operation of the device, respectively, and the removal rates were 34.08%, 55.58% and 58.33%, respectively. During the operation of the system, the TN removal rate of the three groups of devices increased continuously and gradually tended to be stable. It was worth noting that TN removal rate was improved obviously after adding H-PBs, which is similar to the research of Zhao et al. (2019) The study found that the average TN removal rates of CWs with modified canna leaves, modified rice straw, and modified peanut shells were 59.5%, 60.3%, and 61.4%, respectively, which correspondingly increased 17.1–19.0% compared with the control check. Luo et al. (2018) studied the effect of carbon source on nitrogen transformation process and indicated that CWs with husk rice achieved higher removal rate for TN (73–87%) than that of control group. The addition of PBs can improve the TN removal rate because the denitrification process is often inhibited by insufficient carbon sources and lack of anoxic environment. On the one hand, PBs can be used as an organic carbon source to promote the denitrification, On the other hand, an anaerobic environment may form inside the PBs, leading to denitrification. The results indicated that the addition of PBs could improve the denitrification rate and change the nitrification and denitrification capacity of the substrate.
3.3.2 COD removal rate in BRCs
Figure 5d. showed the impact of H-PBs on COD removal in BRCs. Under the conditions of artificial simulated rainfall, the influent concentration was 30 mg/L on average, and the effluent COD concentration was kept below 7 mg/L, leading no effluent water quality deterioration. The COD removal rates of BRC-A and BRC-B showed no significant difference and remained at a high level of about 85%. The BRC-C was in a state of low removal rate at the initial stage, but increased rapidly at the later stage, reaching to 87.98% at 48 d. The reduction of COD in BRCs mainly depends on the decomposition and utilization of microorganisms. Therefore, the main reason accounting for the increase of COD removal efficiency of the three groups in the later stage may be that the reproduction of microorganisms enhanced the assimilation of organic matter. However, the low COD removal rate in the BRC-C at the early stage is related to the large amount of carbon released from the PBs at the early stage after the hydrothermal treatment, increasing the COD load of the system. With the operation of the device, the microorganisms in the system were multiplied, the denitrification of the BRC-C was continuously strengthened, with carbon source continuously being needed. So the COD released by the PBs was utilized and degraded, making the COD removal rate of the BRC-C show an increasing trend. The decreased COD was utilized by both denitrifying microbes and other heterotrophic bacteria (Li et al., 2019). Also, the removal rate of COD in BRC-C increased sharply in the initial stage (5–20 d)and then became stable, this result can be explained by rapid consumption of organics by aerobic microbes in the initial phase under conditions of adequate DO, followed by slow degradation in anaerobic phase (Ong et al., 2010).