Removal of heavy metals from anaerobically digested sewage sludge by isolated indigenous iron-oxidizing bacteria

The removal of heavy metals (Cr, Cu, Zn, Ni and Pb) from anaerobically digested sludge from the Yuen Long wastewater treatment plant, Hong Kong, has been studied in a batch system using isolated indigenous iron-oxidizing bacteria. The inoculation of indigenous iron-oxidizing bacteria and the addition of FeSO4 accelerated the solubilization of Cr, Cu, Zn, Ni and Pb from the sludge. pH of the sludge decreased with an increase in Fe2+ concentrations and reached a low pH of 2-2.5 for treatments receiving both bacterial inoculation and FeSO4. After 16 days of bioleaching, the following heavy metal removal efficiencies were obtained: Cr 55.3%, Cu 91.5%, Zn 83.3%, Ni 54.4%, and Pb 16.2%. In contrast, only 2.6% of Cr, 42.9% of Cu, 72.1% of Zn, 22.8% of Ni and 0.56% of Pb were extracted from the control without the bacterial inoculation and addition of FeSO4. The residual heavy metal content in the leached sludge was acceptable for unrestricted use for agriculture. The experimental results confirmed the effectiveness of using the isolated iron-oxidizing bacteria for the removal of heavy metals from sewage sludge.     

Degradation of inhibitory substances by heterotrophic microorganisms during bioleaching of heavy metals from anaerobically digested sewage sludge

The presence of organic acids was found to be inhibitory to the bioleaching of sewage sludge and the objective of the present study was to elucidate the roles of heterotrophic microorganisms in removing organic acids during the bioleaching of heavy metals from anaerobically digested sewage sludge. Microbiological analysis showed that acetic and propionic acids posed a severe inhibitory effect on iron-oxidizing bacteria as reflected by a sharp decrease in their viable counts in the first 4d and it only started to increase 2d after the depletion of both acids. Biodegradation of these inhibitory organic acids was revealed by sharp increases in total fungi and acidophiles between day 3 and day 5 which coincided with degradation of organic acids. This was further confirmed by the increases in total counts of both acetate and propionate degraders in the same period. Two yeast strains Y4 and Y5 with strong ability to degrade acetate and/or propionate were isolated and identified as Pichia sp. and Blastoschizomycetes capitatus, respectively. B. capitatus Y5 was an more important player in removing the inhibitory organic acids during the bioleaching process since it could utilize both acetate and propionate as sole carbon source while Pichia sp. Y4 was an strict acetate degrader. Results from the present study not only provided the evidence for biodegradation of organic acids by heterotrophs, but also disclosed a biological mechanism for the initiation of bioleaching of organic acid-laden sewage sludge.     

Heavy metals removal from anaerobically digested sludge by chemical and microbiological methods

The metal removal from anaerobically digested sludge was studied by chemical treatment and microbial leaching processes in laboratory reactors. The removal of metals increased with decreased sludge solid concentration and pH. In the acid treatment process, a pH of 1.5 was required to reduce the copper concentration in the sludge to an acceptable level. In the microbial processes mixed culture gave 10% better solubilisation of metals than in single culture. The acid requirement was lower for the microbial process. The cost of sludge treatment in terms of chemicals was found to be decreased by 80% in microbial leaching.     

污泥中氧化硫硫杆菌的分离及其应用效果

以硫粉为能源物质,采用Waksman液体培养基培养,然后以Waksman固体培养基平板接种法直接从污泥中分离出1株高度嗜酸的氧化硫硫杆菌(Thiobacillus thiooxidan).该菌株适应环境速度快,易于驯化.序批式试验法研究表明,接种该菌株进行污泥生物淋滤可有效溶出污泥中的重金属.经过14 d的生物淋滤,Zn、Cu、Pb、Cr的最高去除率分别达到97%、96%、43%、44%.     

Nitrification of centrate from dewatering of anaerobically digested sludge

Nitrification of anaerobically digested sludge centrate was studied in bench-scale suspended growth and fixed film enhanced suspended growth systems at temperatures of 10.5-28.5°C and pH values of 6.0-9.1. Nitrification followed zero-order kinetics in both systems, and ammonia removals in excess of 99% were observed. The temperature dependency of the suspended growth nitrification rate observed under not fully acclimated biomass conditions at pH between 6.8 and 8.5, was expressed as k_T = k₂₀θ^T-20where k₂₀ and θ were found to be 0.34 mg NH₃-N/MLVSS-d and 1.033, respectively. The nitrification rate in the fixed film enhanced suspended growth system involving styrofoam pads ranged from 0.11 to 0.13 mg NH₃-N/mg MLVSS-d at temperatures of 21.5-25°C and pH values of 7.8-8.6. The process contained suspended solids in the range of 10-20 mg/l.     

氧化硫硫杆菌JJU-1生物淋滤去除污泥中的重金属

将前期分离得到的嗜酸性氧化硫硫杆菌JJU-1（Thiobacillus thiooxidans JJU-1）接种于污水处理厂污泥中,进行为期7 d的生物淋滤实验,对淋滤过程中的pH值、氧化还原电位（ORP）和重金属去除率进行检测。研究结果表明：氧化硫硫杆菌JJU-1不同接种量处理浸出液的pH下降幅度不同,当接种量为15%时,浸出液pH下降最快,其ORP达到最大值（444 mV）,Cu、Cd和Pb的去除率分别高达79.2%、96.6%和93.4%。添加能源物质S可以明显降低淋滤液的pH,当能源物质S投入量增加到12 g·L-1时,淋滤7 d后,浸出液的pH下降至1以下,浸出液的ORP在S添加量为16 g·L-1时达到最大值（477 mV）,20 g·L-1 S粉添加量条件下,Cr、Cu和Pb的去除率最大,分别为98.8%、74.3%和85.8%;然而,添加能源物质S对Cd的浸出无明显影响。以上研究结果表明,氧化硫硫杆菌JJU-1在去除污泥中重金属方面有着广阔的前景。     

污水污泥中重金属污染物的溶出过程研究

污水污泥中污染物尤其是重金属的水体浸出作为重要的二次污染途径备受关注。为了探讨污水污泥中重金属的溶出规律,对上海7个污水处理厂的污水污泥进行了重金属总量分析,并采用水平振荡法对上述污水污泥中重金属进行了溶出动力学研究。结果表明,污水污泥中Cu、Cr和Zn的含量均较高,之后依次是Pb、As、Cd和Hg;污水污泥中重金属溶出动力学过程分为快速反应和慢速反应两个过程,可以用Elovich方程进行模拟;污水污泥中各重金属的溶出负荷差异较大,Cu、Cr和Zn的溶出负荷较大,其他较小,但各重金属相对于污水污泥中重金属总量的溶出百分比差异不大,基本处于10%以下。     

Bioleaching of heavy metals from livestock sludge by indigenous sulfur-oxidizing bacteria: effects of sludge solids concentration

A technologically and economically feasible process called bioleaching was used for the removal of heavy metals from livestock sludge with indigenous sulfur-oxidizing bacteria in this study. The effects of sludge solids concentration on the bioleaching process were examined in a batch bioreactor. Due to the buffering capacity of sludge solids, the rates of pH reduction, ORP rise and metal solubilization were reduced with the increase of the solids concentration. No apparent influence of solids concentration on sulfate produced by sulfur-oxidizing bacteria was observed when the solids concentration was less than 4% (w/v). A Michaelis-Menten type of equation was able to well describe the relationship between solids concentration and rate of metal solubilization. Besides, high efficiencies of metal solubilization were achieved after 16 d of bioleaching. Therefore, the bioleaching process used in this study could be applied to remove heavy metals effectively from the livestock sludge.     

生物沥浸法去除猪粪中重金属的研究

探讨以猪粪为培养介质,驯化和加富培养获得硫细菌混合菌液,并研究其对猪粪中重金属的生物沥浸效果。结果表明：猪粪可以在18 d内完成驯化,经3轮富集培养的猪粪粪液可作为硫细菌接种菌液。采用此菌液对猪粪粪液接种并投加硫粉,经过9 d的生物沥浸,Cu、Zn和Cd的沥出率分别达到93.0%、90.1%和67.8%。     

Generation pattern of sulfur containing gases from anaerobically digested sludge cakes.

Eleven dewatered sludge cakes collected from anaerobic digesters at different treatment plants were evaluated for the amount, type, and pattern of odorous gas production. All but one of the sludge cakes were from mesophilic anaerobic digesters. One was from a thermophilic digester. The pattern and quantities of sulfur gases were found to be unique for each of the samples with regard to the products produced, magnitude, and subsequent decline. The main odor-causing chemicals were volatile sulfur compounds, which included hydrogen sulfide, methanethiol, and dimethyl sulfide. Volatile sulfur compound production peaked in 3 to 8 days and then declined. The decline was a result of conversion of organic sulfur compounds to sulfide. In one side-by-side test, a high-solids centrifuge cake generated more odorous compounds than the low-solids centrifuge cake. The data show that anaerobic digestion does not eliminate the odor potential of anaerobically digested dewatered cakes.     

生物淋滤技术对城市污泥中高浓度重金属的去除

实验以单质硫粉作为能源基质,考查了生物淋滤技术针对城市污泥中高浓度重金属的去除效果,探讨了生物淋滤处置前后污泥中重金属的形态变化规律。结果表明,生物淋滤技术能够有效去除污泥中的高浓度重金属。在硫粉投加量为4 g·L-1、HRT为5 d、污泥回流比为50%、污泥浓度为4%、温度为30℃的条件下,生物淋滤系统pH值可降低至1.5左右,污泥中残留重金属Zn、Cu、Cr、Ni分别可降低至400、400、900和200 mg·kg-1左右,达到了《城镇污水处理厂污泥处置林地用泥质》（CJ/T 362-2011）标准重金属限值。生物淋滤处置后,污泥中残留重金属Zn、Cu、Cr、Ni均主要以稳定形态存在,环境风险较低,为进行土地利用奠定了物质基础。     

污泥淋溶器的改进对重金属淋溶行为的影响

为增强污泥淋溶器固定污泥重金属的效果,降低其淋滤液中重金属含量从而更加安全地农业利用,在前期研究基础上对污泥淋溶器进行了改进,实验不同高度开孔和在污泥中间垂直放置黑网两个改进措施。研究表明,距淋溶器底部2 cm处开孔,污泥淋滤液的Cd和Cu总量显著低于底部开孔(原始污泥淋溶器)。淋溶器底部2 cm 形成厌(缺)氧层使得下层硫化物态Zn、Cd和Cu含量显著高于孔的上层,提高了污泥重金属的生物稳定性。添加中间黑网可显著降低污泥淋滤液Cu总量。上述污泥淋溶器的两个改进措施均可有效固定污泥中某些重金属,减小污泥淋滤液重金属累计总量,促进污泥淋滤液更安全农用。     

嗜酸硫杆菌和黑曲霉对电镀污泥重金属浸出效果

电镀污泥重金属浸出对电镀污泥资源化利用具有重要意义。为了降低处置成本,采用嗜酸硫杆菌与黑曲霉对电镀污泥重金属浸出效果进行了研究。结果表明,采用嗜酸性氧化硫硫杆菌和氧化亚铁硫杆菌混合菌种对含固率为3%的电镀污泥进行为期15 d（培养驯化后）的处理后,污泥中Ni、Cr与Cu的浸出率虽分别高达92.8%、85.0%和96.8%,但耗时久,无法大规模地实际应用。利用黑曲霉对电镀污泥进行为期6 d的处理,Ni、Cr和Cu的浸出率分别达到92.0%、74.4%和55.3%。若采用黑曲霉培养15 d后产生的生物有机酸和同pH的柠檬酸处理电镀污泥4 h后,两者对Ni、Cr和Cu的浸出率分别为：85.0%与94.2%、63.8%与73.7%、57.9%与99.6%。可见,利用黑曲霉发酵菌液浸出电镀污泥中重金属有一定的实际应用价值。     

Pyrolysis of humic acids from digested and composted sewage sludge

Humic acids (HAs) were extracted from four digested sewage sludge samples composted for four months, one, two and four years. HAs were pyrolyzed at three different temperatures applying both conventional and in situ methylation (ISM) pyrolysis. The pyrolysates were analyzed using gas chromatography-mass spectrometry (GC/MS). Derivatization (ISM) and pyrolysis temperature had dramatic effects on the composition and relative amounts of the pyrolysates. Among the derivatized HA fragments aliphatic compounds prevailed under all the pyrolysis conditions tested. Aromatic substances consisting mainly of guaiacyl-type compounds were detected in higher abundances only at elevated temperatures. Without ISM the contribution of aromatic structures to the total pyrogram was considerably greater than that of the aliphatics. Increase of the pyrolysis temperature from 450 degrees C to 600 degrees C had smaller effect on the proportions and composition of the compounds studied than increase from 350 degrees C to 450 degrees C.     

Effect of solids concentration on bacterial leaching of heavy metals from sewage sludge

Microbial metal leaching from sewage sludge (2-9% w/v) was carried out with the iron-oxidizing bacterium Thiobacillus ferrooxidans. Measurements of pH, oxidation-reduction potential, and concentration of Fe2+ indicated that T. ferrooxidans was effective in removing metals from an incubation bath containing less than 5% sludge solids concentration. Specifically, Cu leaching was completely suppressed at a high solids concentration of 9% (w/v). Results indicated that the deactivation of T. ferrooxidans at a high sludge content was mainly due to the presence of inhibiting materials such as organic matter. A mixed culture of sulfur-oxidizing bacteria was obtained by enrichment from anaerobically digested sewage sludge to enhance the efficiency of the microbial leaching process. These bacteria were much more effective in metal leaching than was iron-oxidizing T. ferrooxidans. At 9% (w/v) solids concentration, the leaching efficiencies of Zn and Cu were 78% (2.66 g/kg dry sludge) and 59% (1.36 g/kg dry sludge), respectively. Therefore, when removing heavy metals from the anaerobically digested sewage sludge, the indigenous sulfur-oxidizing bacteria isolated in the current study were more efficient than T. ferrooxidans, especially at high sludge solids concentrations.     

Sequential extraction of heavy metals during composting of sewage sludge

The major limitation of soil application of sewage sludge compost is the total heavy metal contents and their bioavailability to the soil-plant system. This study was conducted to determine the heavy metal speciation and the influence of changing the physico-chemical properties of the medium in the course of composting on the concentrations, bioavailability or chemical forms of Cu, Zn, Pb and Ni in sewage sludge. Principal physical and chemical properties and FTIR spectroscopical characterization of sludge compost during treatment show the stability and maturity of end product. The total metal contents in the final compost were much lower than the limit values of composts to be used as good soil fertilizer. Furthermore, it was observed by using a sequential extraction procedure in sludge compost at different steps of treatment, that a large proportion of the heavy metals were associated to the residual fraction (70-80%) and more resistant fractions to extraction X-NaOH, X-EDTA, X-HNO3 (12-29%). Less than 2% of metals bound to bioavailable fractions X-(KNO3+H2O). Heavy metal distribution and bioavailability show some changes during composting depending on the metal itself and the physico-chemical properties of the medium. Bioavailable fractions of all elements tend to decrease except Ni-H2O. Zn and mainly Cu present more affinity to organic and carbonate fractions. In contrast, Pb is usually preferentially bound to sulfide forms X-HNO3. Nickel shows a significant decrease of organic form. Significant degrees of correlation were found between heavy metal fractions and changes of some selected variables (e.g. pH, ash, organic matter, humic substance) during the course of composting. Mobile fractions of metals are poorly predictable from the total content. The R2 value was significantly increased by the inclusion of other variables such as the amount of organic matter (OM) and pH.     

Leaching of heavy metals and alkylphenolic compounds from fresh and dried sewage sludge

Reusing sewage sludge as a soil fertiliser has become a common alternative to disposal. Although this practice has a few benefits, it may contribute to the medium- and long-term contamination of the trophic chain because sewage sludge may contain heavy metals and organic contaminants. As the leaching of contaminants may depend on the sludge pre-treatment, the leaching of heavy metals (Cu, Ni, Pb, Zn and Cr) and alkylphenolic compounds (APCs) (octylphenol (OP), nonylphenol (NP), nonylphenol-mono-ethoxylate (NP₁EO)) was investigated in five fresh and 40 °C dried sewage sludge samples from north-eastern Spain. FT-IR analyses and full-scan GC-MS chromatograms showed that sludge drying changed the nature of organic compounds leading to changes in their solubility. Moreover, sludge drying led to a higher relative contribution of dissolved organic carbon than the particulate organic carbon in the leachates. Leaching of Pb, Zn and Cr was below 5 % in both fresh and dried sludge samples, whereas Cu and Ni leached at rates up to 12 and 43 %, respectively, in some of the dried sludge samples. The leaching yields of OP, NP and NP₁EO ranged from 1.3 to 35 % for fresh samples, but they decreased from 0.8 to 3.4 % in dried samples. The decrease in the leachability of APCs observed in dried sludge samples might be attributed to the fact that these compounds are associated with particulate organic matter, with significantly lower concentration or even absent in dried sludge than in fresh sludge samples. Therefore, it is recommended to dry the sludge before its disposal.     

元素硫颗粒粒径对污泥重金属生物沥滤的影响

以城市污水处理厂剩余污泥作为处理介质,土著嗜酸氧化硫硫杆菌(Acidithiobacillus thiooxidans,A.thiooxi-dans)为主要沥滤微生物,采用序批式生物沥滤装置,就投加150~725μm的不同粒径元素硫对沥滤的酸化效果、硫酸根产率和重金属去除效果的影响进行了研究。结果表明,在元素硫投配量为3 g/L,曝气强度为1.0 L/(min.L)的条件下,元素硫粒径在165~215μm范围减小时能显著改善污泥酸化速度、提高酸化程度和硫酸根产率。底物元素硫的最佳粒径为165μm,此时沥滤体系pH下降速率为0.85个pH单位/d,硫酸根的产率为454.9 mg/(L.d),沥滤6 d后污泥中高浓度重金属Cu、Zn、Cd的去除率达到70.3%、81.2%、87.8%.     

Speciation of heavy metals during co-composting of sewage sludge with lime

During composting the humification of organic matter will have a significant effect on the physicochemical form of existence of heavy metals. Therefore the present study was conducted to investigate the effect of co-composting sewage sludge with lime on heavy metal speciation and the changes in DTPA extractable metals. Metal speciation was conducted to evaluate the redistribution of Cu, Mn, Ni, Pb and Zn in sewage sludge composted with lime. Sewage sludge was mixed with sawdust in 2:1 (w/w fresh weight) and then composted with lime at 0%, 0.63%, 1% or 1.63% (dry weight) for 100 days. The lime addition did not cause any changes in the different forms of Cu and Mn, but the composting process caused transformations of residual form of Cu and Mn into oxidizable and reducible form, respectively. For Ni, the reducible form was mainly transformed into residual form and lime addition decreased this transformation. Major transformation of different forms of Pb was not found, however the residual form of Pb increased with lime addition. The predominant residual form of Zn was mainly transformed into oxidizable form and the lime addition reduced this transformation. Addition of lime to sewage sludge during composting resulted in lower DTPA extractable metal contents. Therefore, lime is a suitable material to co-compost with sewage sludge to reduce the availability of heavy metals.     

污泥活性炭对复合染料的脱色及其重金属浸出毒性

用自制的污泥活性炭处理亚甲基蓝与酸性品红组成的染料废水,研究了pH、吸附时间、温度等因素对复合组分染料废水脱色率的影响,测试分析了污泥活性炭在处理亚甲基蓝与酸性品红复合组分染料废水过程中的重金属浸出毒性。结果表明:与处理单一组分染料废水相比较,处理复合染料废水时pH的影响较为复杂,2种染料在污泥活性炭上存在竞争吸附,但是污泥活性炭对复合组分染料的脱色效果较好。污泥活性炭对复合染料的吸附过程符合Langmuir型吸附。在处理染料废水的过程中,污泥活性炭中的重金属镉、锌及铬会浸出,重金属镉、锌的浸出浓度符合国家标准,但铬的浸出浓度已接近国家标准上限。