Fate of ah receptor agonists during biological treatment of an industrial sludge containing explosives and pharmaceutical residues

GOAL, SCOPE AND BACKGROUND: Sweden is meeting prohibition for deposition of organic waste from 2005. Since 1 million tons of sludge is produced every year in Sweden and the capacity for incineration does not fill the demands, other methods of sludge management have to be introduced to a higher degree. Two biological treatment alternatives are anaerobic digestion and composting. Different oxygen concentrations result in different microbial degradation pathways and, consequently, in a different quality of the digestion or composting residue, It is therefore necessary to study sludge treatment during different oxygen regimes in order to follow both degradation of compounds and change in toxicity. In this study, an industrial sludge containing explosives and pharmaceutical residues was treated with anaerobic digestion or composting, and the change in toxicity was studied. Nitroaromatic compounds, which are the main ingredients of both pharmaceutical and explosives, are well known to cause cytotoxicity and genotoxicity. However, little data are available concerning sludge with nitroaromatics and any associated dioxin-like activity. Therefore, we studied the sludge before and after the treatments in order to detect any changes in levels of Ah receptor (AhR) agonists using two bioassays for dioxin-like compounds. METHODS: An industrial sludge was treated with anaerobic digestion or composting in small reactors in a semi-continuous manner. The same volume as the feeding volume was taken out daily and stored at -20 degrees C. Sample preparation for the bioassays was done by extraction using organic solvents, followed by clean up with silica gel or sulphuric acid, yielding two fractions. The fractions were dissolved in DMSO and tested in the bioassays. The dioxin-like activity was measured using the DR-CALUX assay with transfected H4IIE rat hepatoma pGudluc cells and an EROD induction assay with RTL-W1 rainbow trout liver cells. RESULTS AND DISCUSSION: The bioassays showed that the sludge contained AhR agonists at levels of TCDD equivalents (TEQs) higher than other sludge types in Sweden. In addition, the TEQ values for the acid resistant fractions increased considerably after anaerobic digestion, resulting in an apparent formation of acid resistant TEQs in the anaerobic reactors. Similar results have been reported from studies of fermented household waste. There was a large difference in effects between the two bioassays, with higher TEQ levels in the RTL-W1 EROD assay than in the DR-CALUX assay. This is possibly due to a more rapid metabolism in rat hepatocytes than in trout hepatocytes or to differences in sensitivities for the AhR agonists in the sludge. It was also demonstrated by GC/FID analysis that the sludge contained high concentrations of nitroaromatics. It is suggested that nitroaromatic metabolites, such as aromatic amines and nitroanilines, are possible candidates for the observed bioassay effects. It was also found that the AhR agonists in the sludge samples were volatile. CONCLUSIONS: The sludge contained fairly high concentrations of volatile AhR agonists. The increase of acid resistant AhR agonist after anaerobic digestion warrants further investigations of the chemical and toxic properties of these compounds and of the mechanisms behind this observation. RECOMMENDATION AND OUTLOOK: This study has pointed out the benefits of using different types of mechanism-specific bioassays when evaluating the change in toxicity by sludge treatment, in which measurement of dioxin-like activity can be a valuable tool. In order to study the recalcitrant properties of the compounds in the sludge using the DR-CALUX assay, the exposure time can be varied between 6 and 24 hours. The properties of the acid-resistant AhR agonists formed in the anaerobic treatment have to be investigated in order to choose the most appropriate method for sludge management.     

纳米Fe3O4对污泥厌氧产沼气性能的影响

对采用共沉淀法制备的纳米Fe₃O₄颗粒进行表征,并探究在中温(35 ℃)厌氧消化过程中纳米Fe₃O₄浓度对产气性能的影响。结果表明:纳米Fe₃O₄浓度为100 mg/L时可使厌氧体系中的氨氮浓度维持在600~1 200 mg/L,pH为7~8,TCOD_Cr以及SCOD_Cr去除率分别提高了8.35%和9.90%;该浓度下厌氧体系中产生的挥发性脂肪酸(VFA)浓度最大,可达4 300 mg/L,且强化了对乙酸的利用;该试验组的产气性能最好,相对于空白组,其累积产气量提高了28.08%,产气周期缩短了2 d,甲烷浓度提高了6%。     

沼液回流对秸秆与污泥混合中温厌氧消化的影响

为了提高秸秆与市政污泥混合厌氧消化的消化产率,以秸秆污泥混合物作为底物,在批次实验中研究不同沼液回流对中温（35 ℃）混合厌氧消化过程的影响。实验采用0% 、20%、30%、40%、50%和60%等6种不同的沼液回流量,分析不同沼液回流量下产气量、甲烷含量、发酵过程氨氮含量、sCOD、总挥发酸（VFAs）的变化情况。结果表明：50%的沼液回流产气量和甲烷产量均最大,分别是1 645 mL和797.5 mL,TS和VS去除率达到17.5%和47.8%,单位VS甲烷产量为613.45 mL·g-1,较未加沼液的发酵瓶提高了37.7%,且无VFAs积累。过高的沼液回流量提升了厌氧反应的氨氮浓度,对厌氧产气过程产生了抑制。50%沼液回流量可以作为秸秆污泥混合厌氧消化最佳回流量。     

微好氧预处理对市政污泥厌氧消化产甲烷的影响

针对目前市政污泥处理资源化与减量化效率低的问题,利用微好氧预处理技术进行预处理,提高其甲烷产量。利用有机物溶出效率、VSS减量、甲烷产量3项指标对预处理效果进行了评价;研究了不同参数条件下微好氧预处理对市政污泥厌氧消化产甲烷的影响;探讨了微好氧预处理对污泥胞外聚合物的影响。结果表明,微好氧预处理可以促进污泥溶解性有机物释放、提高VSS去除率;在最佳反应条件下(曝气强度0.30 m³·(min·m³)⁻¹、预处理时间12 h),相对于未经过预处理的工况,甲烷产量可提高26.77%;微好氧预处理对剩余污泥活性细胞的影响主要发生在胞外聚合物部分,同时也存在对活性微生物的破解作用。市政污泥经过微好氧预处理后,可有效提升后续中温厌氧消化或高温厌氧消化的甲烷产量。     

裹包青贮提高玉米秸秆厌氧消化效率的实验研究

秸秆是重要的沼气工程原料,秸秆预处理对其后续厌氧消化效率影响巨大。采用田间裹包青贮方法,设计3因素正交实验,考察了秸秆含水率、压缩比和添加剂对玉米秸秆发酵时间和厌氧消化产沼气的影响。结果表明:秸秆经过裹包青贮,发酵总时间(total fermentation time,TFT)减少1~2 d,累积产气量达到总产气量的90%所用时间(TFT90%)减少了40%~50%,消化效率明显提高;秸秆含水率对产气效果有明显影响,随着含水率增加,单位总固体(total solid,TS)累计产气量(cumulative biogas yields per TS,CBYT)和沼气日产率(biogas yields rate average day,BYR)由高到低排序为:35%~40%,40%~45%,30%~35%;秸秆压缩比对产气效果有明显影响,随着压缩比的增加,其对CBY和BYR的效应由高到低排序为:185、143与138 kg/m3;添加剂类型对产气效果亦有明显影响,在不同添加剂处理下,其对CBYT和BYR的效应由高到低排序为:尿素处理>甲酸处理>无添加剂处理;正交实验极差分析表明,对CBYT和BYR的影响排序为:含水率﹥压缩比﹥添加剂,其田间裹包青贮进行厌氧发酵的优化组合为:青贮秸秆含水率为35%~40%,压缩比为185 kg/m3,添加剂为营养型,青贮20 d,CBYT和BYR达到最大,分别为646.57 mL/g和173.25 mL/(d·g)。     

牛粪和玉米秸秆厌氧消化产甲烷潜力及动力学

为了评价牛粪和玉米秸秆的产甲烷潜力,研究其厌氧消化过程动力学方程,采用自制序批式厌氧发酵实验装置对某养殖场牛粪和秸秆的最大甲烷生产潜力及其发酵过程进行研究。通过实验研究,测得接种物、牛粪和玉米秸秆的累计甲烷产量分别为64.87、244.0和466.54 mL CH4/g VS。根据实测的产气量变化曲线,按照modified Gompertz equation模型进行方程拟合,牛粪组和玉米秸秆组拟合方程的相关性系数分别为0.983和0.991,表明运用modified Gompertz equation模型预测牛粪和玉米秸秆的产甲烷潜力方法可行。通过对产甲烷过程的动力学研究得到:接种物、牛粪和玉米秸秆的最大产甲烷潜力分别为66.07、213.93和458.57 mL CH4/g VS,与实测值的误差率分别为1.8%、12.3%和1.7%;牛粪和玉米秸秆的最大甲烷日产气率(Rm)和延滞期时间(λ)分别是13.14 mL CH4/(g VS·d)、30.76 mL CH4/(g VS·d)和0.35 d、0.71 d。综上,玉米秸秆厌氧消化的停滞期长,但总产气量和最大甲烷日产期率都比牛粪高。     

污泥预处理强化厌氧水解与产甲烷实验研究

污泥传统厌氧消化因水解瓶颈而导致有机物转化甲烷产率低下。选择适当工况对污泥实施预处理可同时实现对污泥中木质纤维素破稳和污泥微生物细胞破壁,从而释放出较多溶解性COD(SCOD),使有机物水解变得容易进行,最终导致甲烷产率大幅提高。本研究通过热水解(T=150℃,t=30 min)、超声波(P=500 W,t=2 h)、碱解(pH=13,t=2 h)和酸解(pH=2,t=2 h)等4种预处理方式对原污泥实施最优工况预处理,分别获得了50.9%、39.1%、31.0%和22.4%的COD溶出率。对预处理后污泥进行传统条件下(SRT=20 d)厌氧消化,分别获得了53.6%、40%、26.8%和24%的甲烷产率(mL/g VSS)增量。同时,预处理后污泥中木质纤维素类物质降解率亦大大增加。缩短SRT(10 d)会导致传统厌氧消化甲烷产率急剧减少,但是,污泥预处理却非常有利于甲烷产率的提高,因此可通过外在预处理方式来逾越内在厌氧水解的瓶颈。     

固相餐厨垃圾厌氧发酵特性

为了研究固相餐厨垃圾厌氧发酵产甲烷特性,对固相餐厨垃圾进行批式厌氧发酵实验,主要考察了pH、VFA、COD以及纤维素酶活的变化情况,并运用修正Gompertz模型对其产气模型进行动力学拟合.实验结果表明,缓冲溶液的添加可明显促进厌氧发酵产甲烷.在添加缓冲溶液条件下,污泥与餐厨垃圾比例为2∶1,1∶1,2∶3和1∶2时,餐厨垃圾都能很好地进行厌氧发酵产甲烷,最大产甲烷产量分别为594.66、449.74、392.93和333.36 mL/g TS.采用修正Gompertz模型分别对2∶1、1∶1、2∶3和1∶2实验组产甲烷曲线进行拟合,得到产甲烷潜力分别为567.57、437.89、381.12和305.60 mL/g TS,最大产甲烷速率分别为89.38、59.81、47.26和25.80 mL/(d·g VS).对厌氧发酵过程中纤维素酶活的变化进行了研究,结果表明,CMC酶活性在提高餐厨垃圾厌氧发酵过程中纤维素的降解起重要作用.     

电弧流溶胞技术促进污泥厌氧消化

为提高污水厂处理污泥时的厌氧消化速率,利用电弧流溶胞技术处理剩余污泥,研究电弧流溶胞技术对污泥破解预处理效果的影响.实验结果表明,与未经预处理的污泥相比,电弧流溶胞处理能够明显提高污泥厌氧消化效率,增加有机物含量和沼气产量.其中,经处理后的污泥TS、VS剩余量分别降低了8.3%和6.3%,COD增加了11.9%.厌氧系统平均产气量平均增加79.76 L/d,增加率45.82%,甲烷含量增加1.03 L/d,增加率102%.由此说明,电弧流溶胞技术可以提高厌氧消化反应中有机物的去除率,有效促进厌氧消化中污泥的水解过程,显著增加甲烷气体的产生量.在综合考虑运行费用和污泥消化效果的前提下,采取适宜的电弧流强化处理措施有一定的积极意义.     

氨氮浓度对马铃薯加工废水厌氧消化的影响

为考察氨氮浓度对中温厌氧消化处理马铃薯加工废水的影响,通过批式实验,探究该类废水厌氧消化处理的氨氮抑制阈值。结果表明：氨氮浓度为3 000 mg·L⁻¹ (TAN≈3 659 mg·L⁻¹)时,累积产甲烷量降低至276.1 mL·g⁻¹且出现产甲烷迟滞期;氨氮浓度为4 000 mg·L⁻¹ (TAN≈4 468 mg·L⁻¹)时,累积产甲烷量仅为对照组的39.2%,迟滞期明显延长了7.2 d;高浓度氨氮抑制造成了以丙酸为主的VFAs积累和有机物(蛋白质等)降解不完全,这是COD去除率下降的主要原因;VFAs作为氨氮抑制发生时COD的主要组分,其积累可作为马铃薯加工废水厌氧消化过程发生氨氮抑制的指示因子;马铃薯加工废水中温厌氧消化的氨氮阈值约为3 000 mg·L⁻¹。该结果可为马铃薯加工废水的高效处理与资源化利用提供参考。