Effect of wastewater composition on the calcium carbonate precipitation in upflow anaerobic sludge blanket reactors

Calcium carbonate often precipitates in anaerobic reactors treating wastewater with high calcium content. The aim of this paper is to study the effect of wastewater composition on calcium carbonate precipitation in upflow anaerobic sludge blanket (UASB) reactors. Two laboratory-scale UASB reactors were operated with calcium-containing influents using acetate and carbohydrate as substrate, respectively. There was an obvious accumulation of inorganic precipitate observed in the biogranules. Observations via scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS) showed that the acclimated biogranules in the two reactors differed in microstructure. Calcium carbonate was found to have precipitated on the surface of acetate-degrading biogranules, but precipitated at the core of the carbohydrate-degrading biogranules. The results indicated that substrates had significant influence on the location of calcium carbonate precipitation in anaerobic granular sludge, which was expected due to the different methanogens distribution and pH gradient within the granular sludge degrading various substrates. Moreover, the location of calcium carbonate precipitation substantially affected the specific methanogenic activity (SMA) of the granular sludge. The SMA of the acetate-degrading biogranules dropped from \(1.96 gCOD_{CH_4 } \cdot gVSS^{ - 1} \cdot d^{ - 1} \) to \(0.61 gCOD_{CH_4 } \cdot gVSS^{ - 1} \cdot d^{ - 1} \) after 180-d of operation in the reactor. However, the SMA of the carbohydrate-degrading biogranules was not adversely affected by calcium carbonate precipitation.     

潮湿气氛下Ca（OH）2与SO2反应动力学研究

本文用固定床积分反应器研究潮湿气氛下Ｃａ（ＯＨ）２与ＳＯ２的反应动力学。     

活性艳红X-3B的厌氧生物降解与机理

以活性艳红X-3B(RBR)为研究对象,分3个不同浓度组研究其在厌氧颗粒污泥作用下的降解性能,并采用生物降解动力学方程拟合其降解过程,同时利用GC-MS分析RBR的生物降解途径.试验结果表明,RBR在厌氧颗粒污泥中降解性能很好,去除率可达93.67%,且其降解过程符合二级反应动力学,其半衰期约为3.561 h.从GC-MS和UV-可见光谱的分析得出,RBR在厌氧颗粒污泥的作用下偶氮键断裂,且生成的芳香胺类化合物进一步降解为小分子的烃类、酚类、醇类和脂类化合物.     

堆肥处理对污泥腐殖物质组成和光谱学特征的影响

采用凝胶(Sephadex G-75)色谱、荧光光谱和红外光谱法研究了污泥堆肥的HA和FA在堆制前后的组成与结构特征变化．凝胶色谱分析表明,污泥经过63d堆腐后,HA中大分子组分含量明显提高;而FA则由不同分子量物质组成,其中小分子量物质占主要部分,在堆腐以后,FA中大分子物质含量下降30％,小分子量物质含量则相对增加．同时,荧光光谱、红外光谱的结果表明：随着污泥堆肥的进行,HA中有机物不饱和结构的多聚化或联合程度增大,芳香结构物质含量增加;但经过堆制的FA具有更多的结构简单的低分子量物质和更低的芳构化水平．     

污泥中活性铝的溶出及形态分布

利用KCl,NH4Ac,HCl,NaOH四种化学浸提液将污水厂初沉污泥中的活性铝溶出,根据不同的溶出机理,得到铝的委员长中化学形态,进行定量测定,得到污泥中活性铝的形态分布,为污泥的合理利用提供一些信息。     

双碱法脱硫技术研究

脱硫过程主要是二氧经硫与氢氧化钠生发化学反应,反应生成物亚硫酸钠溶于水,含亚硫酸钠的脱硫循环水与投加的氢氧化钙反应可生成氢氧化钠和亚硫酸钙。通过沉淀分离可将难溶钙从循环水中清除,氢氧化钠易溶于水可循环使用,脱硫过程中消耗氢氧化钙。达到脱硫效率高,运行费用低的目的。     

Stabilization of the As-contaminated soil from the metal mining areas in Korea

The stabilization efficiencies of arsenic (As) in contaminated soil were evaluated using various additives such as limestone, steel mill slag, granular ferric hydroxide (GFH), and mine sludge collected from an acid mine drainage treatment system. The soil samples were collected from the Chungyang area, where abandoned Au-Ag mines are located. Toxicity characteristic leaching procedure, synthetic precipitation leaching procedure, sequential extraction analysis, aqua regia digestion, cation exchange capacity, loss on ignition, and particle size distribution were conducted to assess the physical and chemical characteristics of highly arsenic-contaminated soils. The total concentrations of arsenic in the Chungyang area soil ranged up to 145 mg/kg. After the stabilization tests, the removal percentages of dissolved As(III) and As(V) were found to differ from the additives employed. Approximately 80 and 40% of the As(V) and As(III), respectively, were removed with the use of steel mill slag. The addition of limestone had a lesser effect on the removal of arsenic from solution. However, more than 99% of arsenic was removed from solution within 24 h when using GFH and mine sludge, with similar results observed when the contaminated soils were stabilized using GFH and mine sludge. These results suggested that GFH and mine sludge may play a significant role on the arsenic stabilization. Moreover, this result showed that mine sludge can be used as a suitable additive for the stabilization of arsenic.     

Stabilization of the As-contaminated soil from the metal mining areas in Korea

The stabilization efficiencies of arsenic (As) in contaminated soil were evaluated using various additives such as limestone, steel mill slag, granular ferric hydroxide (GFH), and mine sludge collected from an acid mine drainage treatment system. The soil samples were collected from the Chungyang area, where abandoned Au–Ag mines are located. Toxicity characteristic leaching procedure, synthetic precipitation leaching procedure, sequential extraction analysis, aqua regia digestion, cation exchange capacity, loss on ignition, and particle size distribution were conducted to assess the physical and chemical characteristics of highly arsenic-contaminated soils. The total concentrations of arsenic in the Chungyang area soil ranged up to 145 mg/kg. After the stabilization tests, the removal percentages of dissolved As(III) and As(V) were found to differ from the additives employed. Approximately 80 and 40% of the As(V) and As(III), respectively, were removed with the use of steel mill slag. The addition of limestone had a lesser effect on the removal of arsenic from solution. However, more than 99% of arsenic was removed from solution within 24 h when using GFH and mine sludge, with similar results observed when the contaminated soils were stabilized using GFH and mine sludge. These results suggested that GFH and mine sludge may play a significant role on the arsenic stabilization. Moreover, this result showed that mine sludge can be used as a suitable additive for the stabilization of arsenic.     

Variation in humic and fulvic acids during thermal sludge treatment assessed by size fractionation,elementary analysis,and spectroscopic methods

Thermal pretreatment can be applied to sludge anaerobic digestion or dewatering. To analyze the variation in humic substances during thermal sludge treatment, sludge humic and fulvic acids were extracted before and after 30-min thermal treatment at 180℃, and then their contents, molecular weight distributions, elementary compositions, and spectral characteristics were compared. The results showed that the total contents of humic and fulvic acids in the sludge almost remained constant during thermal treatment, but 35% ofhumic and fulvic acids were dissolved from the sludge solids. Moreover, both humic and fulvic acids were partly decomposed and 32% of humic acids were converted to fulvic acids. The median value of the molecular weights of humic acids decreased from 81 to 41 kDa and that of fulvic acids decreased from 15 to 2 kDa. Besides the reduction in molecular size, the chemical structures of humic and fulvic acids also exhibited a slight change, i.e. some oxygen functional groups disappeared and aromatic structures increased after thermal sludge treatment.     

固定化菌藻系统及对污水中氮磷营养盐的净化效果

利用海藻酸钙分别包埋固定小球藻、活性污泥及其两者混合物.研究固定态小球藻与悬浮态小球藻对污水中氮磷营养盐的处理效果,实验结果表明固定态藻对氮磷的去除效果明显优于悬浮态藻,其原因主要由于海藻酸钙凝胶对氮磷的吸附,系统pH值提高引起氨的气提及磷酸盐的沉淀作用.研究固定化藻、同定化活性污泥及共固定化菌藻分别对污水中氮磷营养盐的处理效果,在同等条件下,固定化菌藻对氮磷的去除效果优于固定化活性污泥和固定化藻类.这项研究显示菌藻共生在污水处理中具有较大的潜力.     

Fate of proteins of waste activated sludge during thermal alkali pretreatment in terms of sludge protein recovery

Maillard reaction between reducing sugars and amides happened during pretreatment. Over 90 min of TAH at the optimal condition, 67.59% sludge proteins was solubilized. 15.84% soluble proteins broke down to materials with small molecular weight. Proteins are the major organic component s of waste activated sludge (WAS); the recovery of sludge proteins is economically valuable. To efficiently recover sludge proteins, WAS should undergo hydrolysis pretreatment to fully release proteins from sludge flocs and microbial cells into aqueous phase. One of the most widely used chemical methods for that is thermal alkali hydrolysis (TAH). Here, the soluble protein concentration achieved the highest level over 90 min of TAH pretreatment at 80°C; the sludge floc disintegration and microbial cell destruction were maximized according to the content profiles of bound extracellular polymeric substance (EPS) and ribonucleic acid (RNA) of sludge. Both less proteins broken down to materials with small molecular weight and less melanoidin generated were responsible. TAH pretreatment at 80°C for 90 min resulted in the solubilization of 67.59% of sludge proteins. 34.64% of solubilized proteins was present in soluble high molecular; 1.55% and 4.85% broke down to polypeptides and amino acids. The lost proteins via being converted to ammonium and nitrate nitrogen accounted for 9.44% of solubilized proteins. It was important to understand the fate of sludge proteins during TAH pretreatment in terms of protein recovery, which would be helpful for designing the downstream protein separation method and its potential application.     

Identification and assay of microbial fatty acids during co-composting of active sewage sludge with palm waste by TMAH-thermochemolysis coupled with GC-MS

The fatty acids of two composts of active sludge with palm tree waste were investigated by thermochemolysis coupled to gas chromatography-mass spectrometry. This method (tetramethylammonium hydroxide-pyrolysis-gas chromatography-mass spectrometry) allowed the direct determination of total fatty acids (analysed as fatty acid methyl esters: FAMEs) present in the organic matter of the samples without any separation procedures. Mixture A was 1/3 sludge+2/3 palm waste and mixture B was 1/2 sludge+1/2 palm waste. The level of FAMEs rose by 8.4–33.3% and 10.8–13.4% in mixtures A and B, respectively, after 6 months of co-composting. Branched FAMEs of bacterial origin (iC15:0) rose during the thermophilic phase, in mixture A the aC17:0/aC15:0 ratio increased during the co-composting process, also in mixture B the aC16:0/C16:0 ratio rose but only during the thermophilic phase. All the FAMEs identified showed a drop at the end of co-composting except for C18:0 and C16:0. The stabilisation phase was characterised by a significant rise in the length of the aliphatic chains; the carbon preference index thus increased at the end of the composting process, indicating that the final product was proportionally richer in fatty acids of plant origin.     

废水处理系统中生物聚集体胞外多聚物研究进展

胞外多聚物(Extracellular polymeric substances,EPS)是废水生物处理系统中生物聚集体(包括絮体污泥、生物膜、颗粒污泥等)的重要组成部分,直接包裹于微生物细胞壁外,其理化性质及所处的特殊位置决定了它在生物聚集体中的重要作用.综述了EPS对废水生物处理系统污泥沉降性能、脱水性以及膜生物反应器膜污染影响的相关研究,分析认为EPS组成与结构特性改变污泥表面电位、疏水性等,进而影响污泥沉降与脱水性能、膜污染程度;以好氧颗粒污泥为典型的生物聚集体代表,总结了EPS组分含量与分布对颗粒污泥的形成与结构稳定性的影响,并在EPS提取方法标准化、现代理化技术与分子生物学技术综合分析等方面进行了展望,进一步的研究有望揭示生物絮凝体形成过程EPS的产生与调控机制.     

Calcium carbonate waste from an integrated pulp and paper mill as a potential liming agent

Calcium carbonate is used in large amounts in the pulp and paper industry as a paper filler. When it is manufactured, the calcium carbonate waste is purged from the process. Here we demonstrate that, due to the elevated calcium concentration of 168.5 g kg⁻¹ dry weight (dw), alkaline pH of 12.6 and neutralizing (liming) effect value of 42.4% expressed as Ca equivalents, this waste is a potential liming agent and a pH buffer. The heavy metal concentrations in the waste were lower than the new Finnish limit values for fertilizers used in agriculture, as well as for a material, e.g. ash, used as an earth construction agent. These limit values came into force in March 2007 and in June 2006, respectively.     

蚯蚓-稻壳炭联合堆肥对工业污泥中重金属的影响研究

蚯蚓堆肥相关研究多集中在生活污泥方面,对工业污泥的探索较少。该研究以马鞍山某钢铁污水处理站污泥为例,添加不同比例稻壳炭(2%、4%、8%),设置污泥单独堆肥、稻壳炭与污泥堆肥以及蚯蚓-稻壳炭联合污泥堆肥试验,探索蚯蚓与稻壳炭联合堆肥对工业污泥中重金属形态和生物有效性的影响。研究表明,(1)相比污泥单独堆肥,稻壳炭联合污泥堆肥能增加污泥pH、EC、TP和降低TOC、TN,而蚯蚓联合稻壳炭堆肥污泥可增加TN,并进一步增加污泥EC、TP,显著降低污泥的pH、TOC。(2)稻壳炭堆肥中重金属Zn、Cu、Pb、Cd含量因浓缩效应而上升;而蚯蚓联合稻壳炭堆肥,重金属含量显著下降,添加4%稻壳炭时,重金属Zn、Cu、Pb、Cd质量分数达到最小值,分别为856.64、137.10、158.92、15.48mg·kg-1。(3)重金属形态分析表明,随着稻壳炭比例增加,稻壳炭堆肥中重金属Zn、Cu、Pb、Cd的交换态和碳酸盐结合态转化为残渣态及铁锰氧化态的比例增大,添加8%稻壳炭时DTPA提取的有效态重金属质量分数最低,分别为705.72、47.95、50.43、4.47 mg·kg-1;蚯蚓-稻壳炭联合堆肥会使得污泥中重金属交换态、碳酸盐结合态、铁锰结合态和有机结合态均向残渣态转化,添加4%稻壳炭与蚯蚓的协同转化能力最大,Zn、Cu、Pb、Cd有效态重金属质量分数分别为629.84、38.63、36.76、1.63mg·kg-1,说明稻壳炭添加入蚯蚓堆肥可进一步降低工业污泥中重金属有效性,使重金属钝化。本研究可为稻壳炭联合蚯蚓堆肥处理工业污泥提供参考和科学依据。     

Characterization of value-added chemicals derived from the thermal hydrolysis and wet oxidation of sewage sludge

• Hydrothermal treatment can greatly improve resource recovery from sewage sludge. • tCOD removal during WO was ~55% compared with ~23% after TH. • TOC solubilization during hydrothermal treatment followed first-order kinetics. • Solids and carbon balance confirmed loss of organics during thermal hydrolysis. • Reaction pathways for thermal hydrolysis and wet oxidation are proposed. We evaluated the effect of hydrothermal pretreatments, i.e., thermal hydrolysis (TH) and wet oxidation (WO) on sewage sludge to promote resource recovery. The hydrothermal processes were performed under mild temperature conditions (140°C–180°C) in a high pressure reactor. The reaction in acidic environment (pH= 3.3) suppressed the formation of the color imparting undesirable Maillard’s compounds. The oxidative conditions resulted in higher volatile suspended solids (VSS) reduction (~90%) and chemical oxygen demand (COD) removal (~55%) whereas TH caused VSS and COD removals of ~65% and ~27%, respectively at a temperature of 180°C. During TH, the concentrations of carbohydrates and proteins in treated sludge were 400–1000 mg/L and 1500–2500 mg/L, respectively. Whereas, WO resulted in solids solubilization followed by oxidative degradation of organics into smaller molecular weight carboxylic acids such as acetic acid (~400–500 mg/L). Based on sludge transformation products generated during the hydrothermal pretreatments, simplified reaction pathways are predicted. Finally, the application of macromolecules (such as proteins), VFAs and nutrients present in the treated sludge are also discussed. The future study should focus on the development of economic recovery methods for various value-added compounds.     

Mineralogy and chemistry of urinary stones: patients from North Jordan

Urinary stone diseases are increasing in the Middle East. The majority of urinary stone cases are found in the northern part of the country. Stone samples taken from patients living in the Irbid area were collected from Princess Basma Hospital. The present study concentrates on the mineralogical and chemical composition of the urinary stones and on the effective environmental factors that assist in developing the different types of urinary stones. Using X-ray diffraction techniques, the mineralogical composition of the urinary stones was found to be as follows: oxalate, cholesten, and uric acid, with cystine stones occuring more frequently than the others. Cholesten and calcium oxalate stones are the most dominant types of stones. Calcium oxalate is the most common type of oxalate stone. Calcium oxalate is represented in: whewellite, wheddellite, and calcium carbonate oxalate hydrate minerals, in addition to other minerals such as brushite, ammonium phosphate, vaterite, valleriite, and bobierrite from other types of stones. Bobierrite (phosphate group) is a new mineral reported in urinary stones, and this has not been determined in any previous study worldwide. Apatite (calcium phosphate) is deduced using scanning electron microscope (SEM) images. The SEM technique determined crystal forms and systems, shapes, morphological features, and the names of the minerals forming urine stones, while optical properties are studied by polarizing microscope. X-ray fluorescence technique determined the concentrations of major and some trace elements. It revealed that Ca is the main constituent of the urinary stones, especially those composed of calcium oxalate and calcium phosphate. The concentration of trace elements was Ba = 1.57, P = 3.61, Fe = 1.78, S = 2.08, Zr = 4.63, Mo = 3.92, Cu = 1.89, Co = 1.56, and F = 4.2% and was higher in the urinary stones of Jordanian patients than in foreigners in the country. Questionnaires completed by patients suggest that the most significant factors directly effecting the formation of stones are water, climate conditions, food rich in protein and rich in different chemicals. Moreover, some drugs and diseases might also help in developing other stones.     

Hydrophobic calcium carbonate: an option for the value-added conversion of wastes resulting from biodiesel production

High production cost is the key issue of biodiesel industry nowadays. To low down the cost, using low-quality lipids feedstock is the most effective way. Two-step process is vastly applied to deal with those low-quality lipids to produce biodiesel. However, environmentally unfriendly wastes are formed during the process. Here we use calcium oxide residue and wastewater from biodiesel production to produce nanostructured calcium carbonate (CaCO₃) by carbonation at ambient temperature. The results show that CaCO₃ is hydrophobic and has broccoli-like morphology. It is made up of many uniform nano-rods, and each rod is composed of smaller particles with diameters about 50 nm. The idea of wastes utilization could make the biodiesel production process environmentally friendly, and the income of the produced CaCO₃ could further low down the cost of biodiesel production.     

活性炭辅助微波热解污泥反应条件的试验研究

针对微波不能直接实现原污水污泥高温热解的问题,采用活性炭作为微波能吸收物质辅助污泥热解。对影响污泥热解效能的3个主要因素：污泥样品量、活性炭掺杂量和微波辐射功率,各做了3个水平的考察,得到了试验条件下的最优方案：污泥样品量30g、活性炭掺杂量6g、微波辐射功率1200W。结果表明：在最优试验方案下,污泥能在7min内升至920℃的高温,实现污泥快速、高效热解。通过分析3个因素对污泥热解效能的影响,进一步对最优试验方案下的固体产物吸收微波的性能及用其作为掺杂物辅助微波热解污水污泥的可行性进行了研究,结果表明：固体残渣吸收微波性能良好,可以代替活性炭作为更经济、高效的污泥微波热解辅助材料。     

Possible solutions for sludge dewatering in China

In China, over 1.43×10⁷ tons of dewatered sewage sludge, with 80% water content, were generated from wastewater treatment plants in 2007. About 60% of the COD removed during the wastewater treatment process becomes concentrated as sludge. Traditional disposal methods used by municipal solid waste treatment facilities, such as landfills, composting, or incineration, are unsuitable for sludge disposal because of its high water content. Disposal of sludge has therefore become a major focus of current environmental protection policies. The present status of sludge treatment and disposal methodology is introduced in this paper. Decreasing the energy consumption of sludge dewatering from 80% to 50% has been a key issue for safe and economic sludge disposal. In an analysis of sludge water distribution, thermal drying and hydrothermal conditioning processes are compared. Although thermal drying could result in an almost dry sludge, the energy consumption needed for this process is extremely high. In comparison, hydrothermal technology could achieve dewatered sewage sludge with a 50%–60% water content, which is suitable for composting, incineration, or landfill. The energy consumption of hydrothermal technology is lower than that required for thermal drying.