Enhancing short-term ethanol-type fermentation of waste activated sludge by adding saccharomycetes and the implications for bioenergy and resource recovery

Ethanol-type sludge fermentation has recently attracted much attention because it can enhance direct interspecies electron transfer and thus improve the anaerobic digestion of waste activated sludge(WAS). In this paper, the enhancement of short-term ethanol-type fermentation of WAS via adding Saccharomyces was investigated. The experimental results show that the maximum ethanol production of 1030.8 ± 20.6 mg/L was achieved, with the optimum fermentation conditions of a p H of 5.1, temperature of...     

Effect of nitrite on hydrolysis-acidification, biogas production and microbial community in semi-continuous two-phase anaerobic digestion of sewage sludge

Previous study found that the pre-treatment of sewage sludge with nitrite improves the biogas production during the mono/two-phase anaerobic digestion (AD) using batch biochemical methane potential tests. In this study, the effects of nitrite on hydrolysis-acidification, biogas production, volatile solids destruction and microbial composition in semi-continuous two-phase AD of sewage sludge were investigated. The addition of nitrite promotes sludge organic matter solubilization (+484%) and VFAs production (+98.9%), and causes an increase in the VS degradation rate during the AD process (+8.7%). The comparison of biogas production from the acidogenic and methanogenic reactors with or without the addition of nitrite implies that the nitrite has no significant effect on the overall biogas production of two-phase sludge AD process. High-throughput sequencing analysis shows that the microbial communities of bacteria and archaea in two-phase AD reactors significantly changes after the addition of nitrite. Vulcanibacillus (bacteria) and Candidatus Methanofastidiosum (archaea) become the dominant genera in the acidogenic and methanogenic reactors with the nitrite respectively. These findings provide new insights about using nitrite to promote the organic matter degradation of sewage sludge in a semi-continuous two-phase AD system.     

Enhanced nitrogen removal upon the addition of volatile fatty acids from activated sludge by combining calcium peroxide and low-thermal pretreatments

This study investigated a combined low-thermal and CaO₂ pretreatment to enhance the volatile fatty acid (VFA) production from waste activated sludge (WAS). The fermentative product was added to a sequencing batch reactor (SBR) as an external carbon source to enhance nitrogen removal. The results showed that the combined pretreatment improved WAS solubilization, releasing more biodegradable substrates, such as proteins and polysaccharides, from TB-EPS to LB-EPS and S-EPS. The maximum VFA production of 3529 ± 188 mg COD/L was obtained in the combined pretreatment (0.2 g CaO₂/g VS + 70 °C for 60 min), which was 2.1 and 1.4-fold of that obtained from the sole low-thermal pretreatment and the control test, respectively. Consequently, when the fermentative liquid was added as an external denitrification carbon source, the effluent total nitrogen decreased to Class A of the discharge standard for pollutants in rural wastewater treatment plants in most areas of China.     

基于pH调控的城市污泥厌氧发酵产酸小试研究

本研究设计了热碱预处理-半连续流厌氧发酵污泥处理工艺,探究了p H对热碱预处理污泥产酸性能的影响,同时对发酵液作为碳源回用于污水厂强化脱氮除磷进行了质量衡算.在30 L厌氧发酵罐中考察了偏中性(p H=6.5)和碱性(p H=10.0)条件下热碱预处理污泥发酵的挥发性脂肪酸(VFA)产生及分布、蛋白质及碳水化合物的消耗和氮磷释放情况.结果表明,污泥热碱预处理-半连续流厌氧发酵工艺的VFA产量稳定,在p H为6.5和10.0的条件下,发酵罐中平均VFA产率分别为333.29 mg·g-1(以每g VS产生的COD(mg)计,下同)和250.64 mg·g-1,p H为6.5时产酸更稳定,且产量较高,但碱性条件更适合产乙酸.两种p H条件下的SCOD、溶解性蛋白质、溶解性多糖、氮和磷的释放都无较大差异.质量衡算结果表明,以处理量为50000 m3·d-1的城市污水处理厂为例,其产生的污泥经过热碱预处理-半连续流厌氧发酵产酸工艺,产生的VFA能够满足该污水处理厂脱氮除磷提标改造的碳源需求.     

Potassium ferrate pretreatment promotes short chain fatty acids yield and antibiotics reduction in acidogenic fermentation of sewage sludge

During the acidogenic fermentation converting waste activated sludge (WAS) into short-chain fatty acids (SCFA), hydrolysis of complex organic polymers is a limiting step and the transformation of harmful substances (such as antibiotics) during acidogenic fermentation is unknown. In this study, potassium ferrate (K₂FeO₄) oxidation was used as a pretreatment strategy for WAS acidogenic fermentation to increase the hydrolysis of sludge and destruct the harmful antibiotics. Pretreatment with K₂FeO₄ can effectively increase the SCFA production during acidogenic fermentation and change the distribution of SCFA components. With the dosage of 0.2 g/g TS, the maximum SCFA yield was 4823 mg COD/L, which is 28.3 times that of the control group; acetic acid accounts for more than 90% of the total SCFA. The higher dosage (0.5 g/g TS) can further increase the proportion of acetic acid, but inhibit the overall performance of SCFA production. Apart from the promotion of hydrolysis and acidogenesis, K₂FeO₄ pretreatment can also simultaneously oxidizes and degrades part of the antibiotics in the sludge. When the dosage is 0.5 g/g TS, the degradation efficacy of antibiotics is the most significant, and the contents of ofloxacin, azithromycin, and tetracycline in the sludge are reduced by 69%, 42%, and 50%, respectively. In addition, K₂FeO₄ pretreatment can also promote the release of antibiotics from sludge flocs, which is conducive to the simultaneous degradation of antibiotics in the subsequent biological treatment process.     

Effect of manganese oxide-modified biochar addition on methane production and heavy metal speciation during the anaerobic digestion of sewage sludge

Low organic matter content and high heavy metal levels severely inhibit the anaerobic digestion (AD) of sewage sludge. In this study, the effect of added manganese oxide-modified biochar composite (MBC) on methane production and heavy metal fractionation during sewage sludge AD was examined. The MBC could increase the buffering capacity, enhance the methane production and degradation of intermediate acids, buffer the pH of the culture, and stabilize the sewage sludge AD process. The application of MBC positively impacted methane production and the cumulative methane yield increased up to 121.97%, as compared with the control. The MBC addition can improve metal stabilization in the digestate. An optimum MBC dose of 2.36?g was recommended, which would produce up to 121.1?L/kg volatile solids of methane. After the AD process, even though most of the metals accumulated in the residual solids, they could be transformation from the bio-available fractions to a more stable fraction. The total organic- and sulfide-bound and residual fraction content at a 3?g dose of MBC that is 0.12?g/g dry matter were 51.06% and 35.11% higher than the control, respectively. The results indicated that the application of MBC could improve the performance of AD and promote stabilization of heavy metals in sewage sludge post the AD process.     

Flow analysis of major and trace elements in residues from large-scale sewage sludge incineration

Increase of sewage sludge (SS) has led to the construction of more incineration plants, exacerbating to the production of SS incineration residues. However, few studies have considered the mass balance of elements in large-scale SS incineration plants, affecting the residues treatment and utilization. In this study, flow analysis was conducted for major and trace elements in the SS, the fly ash (sewage sludge ash, SSA) and bottom ash from two large-scale SS incineration plants. The elemental characteristics were compared with those of coal fly ash (CFA), and air pollution control residues from municipal solid waste incineration (MSWIA), as well as related criteria. The results showed that the most abundant major element in SSA was Si, ranging from 120 to 240 g/kg, followed by Al (76–348 g/kg), Ca (26–113 g/kg), Fe (35–80 g/kg), and P (26–104 g/kg), and the trace elements were mainly Zn, Ba, Cu, and Mn. Not all the major elements were derived from SS. Most trace elements in the SS incineration residues accounted for 82.4%–127% of those from SS, indicating that SS was the main source of trace elements. The partitioning of heavy metals in the SS incineration residues showed that electrostatic precipitator ash or cyclone ash with high production rates were the major pollutant sinks. The differences in some major and trace elements could be indicators to differentiate SSA from CFA and MSWIA. Compared with related land criteria, the pollutants in SSA should not be ignored during disposal and utilization.     

Effects of free ammonia on volatile fatty acid accumulation and process performance in the anaerobic digestion of two typical bio-wastes

The effect of free ammonia on volatile fatty acid(VFA)accumulation and process instability was studied using a lab-scale anaerobic digester fed by two typical bio-wastes:fruit and vegetable waste(FVW)and food waste(FW)at 35°C with an organic loading rate(OLR)of 3.0 kg VS/(m~3·day). The inhibitory effects of free ammonia on methanogenesis were observed due to the low C/N ratio of each substrate(15.6 and 17.2,respectively). A high concentration of free ammonia inhibited methanogenesis resulting in the accumulation of VFAs and a low methane yield. In the inhibited state,acetate accumulated more quickly than propionate and was the main type of accumulated VFA. The co-accumulation of ammonia and VFAs led to an "inhibited steady state" and the ammonia was the main inhibitory substance that triggered the process perturbation. By statistical significance test and VFA fluctuation ratio analysis,the free ammonia inhibition threshold was identified as 45 mg/L. Moreover,propionate,iso-butyrate and valerate were determined to be the three most sensitive VFA parameters that were subject to ammonia inhibition.     

污泥厌氧发酵产酸关键影响因素的函数模型研究

本研究以城市剩余污泥预处理液作为底物,调节底物不同C/N比,测定了厌氧发酵过程中几种关键酶的酶活及发酵产物乙酸、丙酸及丁酸的浓度.同时,利用Matlab软件通过回归分析和函数拟合构建了C/N比-关键酶活-酸产量之间的多项式函数模型,发现所建立的二元三次多项式模型的拟合优度R2均大于0.9,且残差平方和较小,因此,判定二元三次多项式更适合描述C/N比-关键酶活-酸产量的数学关系.最后,建立了关键酶活、C/N比和产酸量三因素间的曲面模型,发现该模型能够很好地描述污泥厌氧发酵中C/N比条件对关键酶和产酸类型的影响,并能进一步预测C/N比所对应的酶活和产酸发酵类型,可为今后的实验研究及工程放大提供理论参考.     

Optimizing food waste hydrothermal parameters to reduce Maillard reaction and increase volatile fatty acid production

The occurrence of the Maillard reaction and melanoidins formation during the hydrothermal treatment of food waste can reduce the yield of volatile fatty acids (VFA); however, few studies have investigated the adverse effects of the Maillard reaction. This study identified the impact of hydrothermal treatment parameters on hydrolysis and melanoidins formation and optimized the hydrothermal treatment conditions to enhance VFA production by minimizing the impact of the Maillard reaction. A response surface methodology was employed to optimize the hydrothermal treatment parameters and VFA production was evaluated. Results showed that temperature, reaction time, and pH were significant interacting factors with respect to hydrolysis and melanoidins formation while the C/N ratio and moisture content of food waste had little impact. The optimal conditions for hydrothermal treatment (temperature of 132 °C, reaction time of 27 min, and a pH of 5.6) enhanced VFA production by 22.1%. Under optimal hydrothermal treatment conditions, a higher initial C/N ratio further increased VFA production.     

Mechanisms of allicin exposure for the sludge fermentation enhancement: Focusing on the fermentation processes and microbial metabolic traits

As a frequently used product with antimicrobial activity, consumed allicin might be discharged and concentrated in waste-activated sludge (WAS). However, the influence of allicin (as an exogenous pollutant) on WAS fermentation has not been clearly revealed. This study aimed to disclose the impacts of allicin on volatile fatty acid (VFA) generation during WAS fermentation. The results showed that the appropriate presence of allicin (10 mg/g TSS) significantly enhanced the VFA yield (1894 versus 575 mg COD/L in the control) with increased acetate proportion (24.3%). Further exploration found that allicin promoted WAS solubilization, hydrolysis and acidification simultaneously. Metagenomic analysis revealed that the key genes involved in extracellular hydrolysis metabolism (i.e., CAZymes), membrane transport (i.e., gtsA and ytfT), substrate metabolism (i.e., yhdR and pfkC) and fatty acid synthesis (i.e., accA and accD) were all highly expressed. Allicin also induced the bacteria to produce more signalling molecules and regulate cellular functions, thereby enhancing the microbial adaptive and regulatory capacity to the unfavourable environment. Moreover, the variations in fermentative microbes and their contributions to the upregulation of functional genes (i.e., ytfR, gltL, INV, iolD and pflD) for VFA generation were disclosed. Overall, the simultaneous stimulation of functional microbial abundances and metabolic activities contributed to VFA production in allicin-conditioned reactors.     

A novel online analyzer for accurate and rapid measurement of volatile fatty acids in anaerobic wastewater treatment

Volatile fatty acids (VFAs), which are largely generated during the anaerobic acidification process, are considered to be reliable indicators of the stable process operation. However, the common methods for monitoring VFAs are offline, and they are typically manual requiring time-consuming, costly and complex instruments. This study aims to develop a novel online analyzer for automatic measuring VFAs, which was based on the 5-pH point titration, embedded with a proportional-integral-derivative (PID) feedback control system. The results show that it can achieve accurate and rapid monitoring of VFAs ranging between 0-400 mg/L (<9 min/sample) but simultaneously faces the problems of overtitration and interference of complex characteristics of wastewater. In order to improve its accuracy and stability, the effects of three general coefficients (K_I, K_P, and K_D) of PID on the titration were investigated, and the optimal values of K_I, K_P, and K_D were found to be 1.5, 1.0, and -1.0~0.5, respectively. Besides, the initial titration speed was set at 0.06 mL/min, equal to the minimum speed of the peristaltic pump, and the dichotomy approach was integrated into the PID feedback controller. Owing to the above improvements, the relative mean deviation and standard deviation of measuring VFAs in both synthetic and real wastewaters were mostly lower than 5.0% and 5.0 mg/L, proving the online analyzer is rapid, accurate and reliable.     

Effects of sludge age on anaerobic acidification of waste activated sludge: Volatile fatty acids production and phosphorus release

Effects of sludge age on volatile fatty acids (VFAs) production and Phosphorus (P) release during anaerobic acidification of waste activated sludge (WAS) were investigated. Sequencing batch reactors (SBR) fed with simulating domestic sewage were applied to produce WAS of different sludge ages, and batch tests were used for anaerobic acidification. The maximum dissolved total organic carbon, release of  ${\text{PO}}_4^{3+}?\mathrm{P}$, and accumulation of acetate (C2), propionate (C3), butyrate (C4), and valerate (C5) decreased by 56.2%, 55.8%, 52.6%, 43.7%, 82.4% and 84.8%, respectively, as the sludge age of WAS increased from 5 to 40 days. Limited degradation of protein played a dominating role in decreasing DTOC and VFAs production. Moreover, the increase in molecular weight of organics and organic nitrogen content in the supernatant after acidification suggested that the refractory protein in WAS increased as sludge age extended. Although the production of C2, C3, C4, and C5 from WAS decreased as the sludge age increased, the proportions of C2 and C3 in VFAs increased, which might be due to the declined production of C5 from protein and the faded genus Dechlorobacter. Keeping sludge age of WAS at a relatively low level (<10 days) is more appropriate for anaerobic acidification of WAS as internal carbon sources and P resource.     

Transformation and migration of phosphorus in excess sludge reduction pretreatment by alkaline ferrate oxidation combined with anaerobic digestion

Recently,more and more attention has been paid to the strong oxidation ability of newly prepared potassium ferrate(NAPF) in sludge reduction process,but less attention has been paid to the change of phosphorus in this process.The feasibility of phosphorus migration and transformation during excess sludge reduction pretre atment using NAPF pre-oxidation combined with anaerobic digestion was investigated.After 70 mg/g suspended solids NAPF pretreatment and 16 days anaerobic digestion,the solid-phase volatile suspended solids decreased by 44.2%,and much organic matter had been released into the liquid-phase and then degraded during digestion by indigenous microorganisms.As the sludge pre-oxidation process was performed,solid-phase organic phosphorus and chemically combined phosphorus also released into the liquid-phase as PO_4~(3-),peaking at 100 mg/L.During anaerobic digestion,the Fe~(3+)in the liquid-phase was gradually reduced to Fe~(2+),and then formed Fe~(2+)-PO_4~(3-) compound crystals and re-migrated to the solid-phase.The concentration of PO_4~(3-) decreased to 17.08± 1.1 mg/L in the liquid-phase after anaerobic digestion.Finally,the phosphorus in the Fe~(2+)-PO_4~(3-) compound accounts for 80% of the total phosphorus in the solid-phase.A large number of vivianite crystals in sludge were observed.Therefore,this technology not only effectively reduces sludge,but also increases the proportion of PO_4~(3-)in the sludge in the form of Vivianite.     

C/N对污泥厌氧发酵产酸类型及代谢途径的影响

研究了污泥的初始C/N对污泥发酵产酸类型的影响及产酸代谢途径.初始C/N在12时,形成的是乙酸型发酵类型;当初始C/N在56左右,可实现丙酸型发酵类型;而当C/N处于156时,则形成丁酸型发酵.不同发酵产酸类型的形成是由优势产酸菌群的改变导致的.末端限制性片段长度多态性分析(T-RFLP)微生物种群的结果表明,构成乙酸型发酵类型的主要优势菌群为消化链球菌属;而丙酸型发酵类型中的优势菌群则为丙酸杆菌属;梭菌属则是丁酸型发酵类型中的优势产酸功能菌.有机酸代谢途径中关键酶活性检测结果表明,在低C/N条件下,乙酸的累积主要是通过氨基酸之间的Stickland反应形成,而随着C/N值的增大,导致丙酸和丁酸累积的主要代谢途径转变为糖酵解的丙酮酸途径.     

pH值调控对柑橘废渣与污泥厌氧共发酵产酸影响

为提高挥发性脂肪酸(VFA)的产量,探究了柑橘废渣和剩余污泥不同VS(挥发性固体)配比及调控发酵过程pH值对产VFA性能的影响.结果表明:调节共发酵系统pH值为6对VFA的积累有促进作用,柑橘废渣VS/剩余污泥VS为2时的最大VFA产量为11183.12mg/L,是未控制pH值组最高VFA浓度的1.75倍.柑橘废渣中的...     

Characterization of sulfide oxidation and optimization of sulfate production by a thermophilic Paenibacillus naphthalenovorans LYH-3 isolated from sewage sludge composting

The sulfur-containing odor emitted from sludge composting could be controlled by sulfide oxidizing bacteria, yet mesophilic strains show inactivation during the thermophilic stage of composting. Aimed to investigate and characterize the thermotolerant bacterium that could oxidize sulfide into sulfate, a heterotrophic strain was isolated from sewage sludge composting and identified as Paenibacillus naphthalenovorans LYH-3. The effects of various environmental factors on sulfide oxidation capacities were studied to optimize the sulfate production, and the highest production rate (27.35% ± 0.86%) was obtained at pH 7.34, the rotation speed of 161.14 r/min, and the inoculation amount of 5.83% by employing Box-Behnken design. The results of serial sulfide substrates experiments indicated that strain LYH-3 could survive up to 400 mg/L of sulfide with the highest sulfide removal rate (88.79% ± 0.35%) obtained at 50 mg/L of sulfide. Growth kinetic analysis presented the maximum specific growth rate µ_m (0.5274 hr⁻¹) after 22 hr cultivation at 50°C. The highest enzyme activities of sulfide quinone oxidoreductase (0.369 ± 0.052 U/mg) and sulfur dioxygenase (0.255 ± 0.014 U/mg) were both obtained at 40°C, and the highest enzyme activity of sulfite acceptor oxidoreductase (1.302 ± 0.035 U/mg) was assessed at 50°C. The results indicated that P. naphthalenovorans possessed a rapid growth rate and efficient sulfide oxidation capacities under thermophilic conditions, promising a potential application in controlling sulfur-containing odors during the thermophilic stage of sludge composting.     

Functionalization of nitrogen-doped graphene quantum dot: A sustainable carbon-based catalyst for the production of cyclic carbonate from epoxide and CO2

A series of organic compounds were successfully immobilized on an N-doped graphene quantum dot (N-GQD) to prepare a multifunctional organocatalyst for coupling reaction between CO₂ and propylene oxide (PO). The simultaneous presence of halide ions in conjunction with acidic- and basic-functional groups on the surface of the nanoparticles makes them highly active for the production of propylene carbonate (PC). The effects of variables such as catalyst loading, reaction temperature, and structure of substituents are discussed. The proposed catalysts were characterized by different techniques, including Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy/energy dispersive X-ray microanalysis (FESEM/EDX), thermogravimetric analysis (TGA), elemental analysis, atomic force microscopy (AFM), and ultraviolet–visible (UV-Vis) spectroscopy. Under optimal reaction conditions, 3-bromopropionic acid (BPA) immobilized on N-GQD showed a remarkable activity, affording the highest yield of 98% at 140°C and 10⁶ Pa without any co-catalyst or solvent. These new metal-free catalysts have the advantage of easy separation and reuse several times. Based on the experimental data, a plausible reaction mechanism is suggested, where the hydrogen bonding donors and halogen ion can activate the epoxide, and amine functional groups play a vital role in CO₂ adsorption.