Effect of reducing conditions on sludge melting process

The objective of this study was to compare the effects of CO/CO(2) reducing conditions with those of air oxidizing conditions on the pouring temperature of the sludge melting process and the heavy metal leachability of the resultant sludge slag. Synthetic sludge ash composed of SiO(2), CaO and Al(2)O(3), as well as sewage sludge ash generated from a laboratory incinerator was employed. The experimental results indicated that the pouring temperatures are significantly reduced under the reducing conditions of CO/CO(2), or 24 and 77 degrees C lower than under air conditions for synthetic and sludge ash, respectively. The heavy metal leaching tests further indicate lower heavy metal concentrations present in the leachate under the reducing conditions, notably an order of magnitude lower in Zn. However, X-ray diffractogram indicates similar peaks for these two slags produced under different conditions.     

Waste recycling of cathode ray tube glass through industrial production of transparent ceramic frits

ABSTRACT

Cathode ray tube (CRT) glass contains significant amounts of alkali and alkaline earth oxides, making it a useful by-product for use in the ceramics industry. Among the various alkali oxides present, those of strontium (SrO), calcium (CaO), and magnesium (MgO) are well known flux materials used widely in the ceramics industry. The most effective flux, SrO, is also a limited resource. In this study, we aimed to develop an environmentally friendly, low-cost method for recycling CRT waste by using it to produce transparent ceramic frits on an industrial scale. Four different samples were fabricated containing between 13 and 25 wt.% CRT panel glass. The color values, sintering behaviors, phases, and microstructural properties of the corresponding samples were analyzed and compared. The results indicate that a composition containing 25 wt.% CRT panel glass could pass the ISO 10545 test. Thus, the results confirm that CRT glass can be used to inexpensively produce transparent ceramic frits at an industrial scale.

Implications: The recycling of electronic waste (e-waste), including CRT waste, has increased by high rates of computer and TV consumption. This increase in consumption is likely to increase the rate at which CRTs are discarded. However, CRTs cannot be recycled in the desired amount. Owing to the high silicate, barium and strontium content of CRTs, it has great potential for glass ceramics such as frits. CRT panel glass to produce commercial transparent frit at low cost through an industrial production route for use in single-fire sintered products. Thus, CRT wastes can be recycled cost-effective, sustainable and environmentally friendly.     

Prevention of struvite scaling in digesters combined with phosphorus removal and recovery--the FIX-Phos process

The fixation of phosphorus (FIX-Phos) combines struvite prevention and phosphorus recovery by the addition of calciumsilicatehydrate (CSH) particles into the anaerobic digester. The CSH fixates phosphorus as calcium phosphate and reduces the phosphorus concentration in the sludge water that allows for control of struvite formation. The phosphorus-containing recovery product can be separated and recovered from the digested sludge. In pilot plant experiments, 21% to 31% of phosphorus contained in digested sludge could be recovered when CSH was added at concentrations of 2 g/L to 3.5 g/L to a mixture of primary sludge and waste activated sludge (WAS) from enhanced biological phosphorus removal. The recovery product contained few heavy metals and a phosphorus content of 18 wt % P2O5, which allows for recycling as fertilizer. The fixation of phosphorus within the digester may increase wastewater sludge dewaterability. The phosphorus recycle stream to the headworks of the wastewater treatment plant is reduced.     

Heavy metal-rich wastes sequester in mineral phases through a glass-ceramic process

Certain sludges generated by industry are rich in contaminating elements and are a major environmental problem. In this study, we determine the ability of these contaminating elements to be incorporated into a glass-matrix and in various mineral phases after a crystallization process. The contaminating elements studied were obtained from sewage sludges (SS) and galvanic sludges (GS), our raw materials. The sludge samples were taken from urban wastewater treatment plant in Catalonia (NE Spain) with high levels of phosphorus oxide (P(2)O(5)). In silica glasses, P(2)O(5) acts as a network former. We determined the chemical composition of both the SS and GS, as well as their thermal behaviour by differential thermal analysis and thermal gravimetric analysis (DTA-TG) to obtain their melting curves. The vitreous transition temperature of the obtained glass was established by dilatometer technique at 725 degrees C. The DTA-TG curve of the glass obtained has an exothermal wide peak at 860 degrees C corresponding to crystallization of the two phases: a spinel phase and a phosphate phase. A second exothermal wide peak at 960 degrees C was attributed to the crystallization of aluminium pyroxene, anorthite and fluor-apatite, with two exothermal phenomena attributed to the evolution of these phases. An exothermal peak at 1100 degrees C was attributed to gehlenite crystallization. Scanning electron microscope observations and energy-dispersed X-ray spectroscopy microanalyses of glass-ceramic showed that the contaminating elements were concentrated in the spinel phases, which are the first phases to crystallize during the cooling of glass. Finally, the spinel structure permits the incorporation of all the contaminating elements into it.     

Ecotoxicity, phytotoxicity and extractability of heavy metals from different stabilised sewage sludges

The presence of heavy metals in the sludges produced in wastewater treatment plants restricts their use for agricultural purposes. This study compares different types of sludges (aerobic, anaerobic, unstabilised and sludge from a waste stabilisation pond) in order to assess the extractability of heavy metals using simple extraction, water and DTPA. The stabilisation treatment undergone by the sludges influenced the heavy metals extractability. The least mineralised sludges (unstabilised and aerobic) showed higher metal extractability. The sewage sludges were subjected to chemical characterisation and toxicity testing (ecotoxicity and phytotoxicity assays) in absence of substrate, to provide a preliminary assessment of their suitability for land application. The ecotoxicity assays confirmed that no sludge constituted a hazardous waste. The sludge extracts had significant adverse effect on the germination index (GI) of barley (Hordeum vulgare L.) and cress (Lepidium sativum L.), a fact which indicates that some characteristics affected root growth.     

Retrieval of heavy metal ions from solution via ferritisation

The paper summarises the results of the studies on retrieval of heavy metal ions in solution by ferritisation and its potential application in waste-water treatment. The optimum procedure for ferritisation of heavy metal ions in solution has been evolved with respect to pH, concentration of Fe2+, rate and time of aeration and temperature. The recommended procedure consists of controlled aeration of the solution containing heavy metal ions and ferrous ions at pH 9.5-10.5 at about 50 degrees C, until the black, granular, magnetic ferrite separates out. The metal ferrites can also be formed, even without heating or forced aeration, by ageing the mixed metal hydroxide precipitate at pH 10 to 11. The metal ferrites formed have been characterised by X-ray diffractometry. The laboratory-scope experiments conducted with synthetic heavy metal solutions as well as actual wastewater from a tanning industry showed that heavy metal ions can be effectively removed from solution to sub-ppm levels. The metal ferrites thus recovered may find commercial application as microwave absorbers, catalysts, metal scavengers, etc. This technique seems to have potential application in simultaneous, one step removal of different heavy metal ions from industrial wastewaters.     

Occurrence and fate of heavy metals in the wastewater treatment process

The occurrence and the fate of heavy metals (Cd, Pb, Mn, Cu, Zn, Fe and Ni) during the wastewater treatment process were investigated in the wastewater treatment plant (WTP) of the city of Thessaloniki, northern Greece, operating in the activated sludge mode. For this purpose, wastewater and sludge samples were collected from six different points of the plant, namely, the influent (raw wastewater, RW), the effluent of the primary sedimentation tank (primary sedimentation effluent, PSE), the effluent of the secondary sedimentation tank (secondary sedimentation effluent, SSE), sludge from the primary sedimentation tank (primary sludge, PS), activated sludge from the recirculation stream (activated sludge, AS), and the digested/dewatered sludge (final sludge, FS).

The distribution of metals between the aqueous and the solid phase of wastewater was investigated. Good exponential correlation was found between the metal partition coefficient, logK_p, and the suspended solids concentration. The mass balance of heavy metals in the primary, secondary and the whole treatment process showed good closures for all metal species. The relative distribution of individual heavy metals in the treated effluent and the sludge streams indicated that Mn and Cu are primarily (>70%) accumulated in the sludge, while 47–63% of Cd, Cr, Pb, Fe, Ni and Zn remain in the treated effluent.     

Sample storage and extraction efficiencies in determination of polycyclic and nitro musks in sewage sludge

Analytical technology is continuously improving, developing better methods for isolating and concentrating trace compounds in environmental samples. Polycyclic and nitro musks (PNMs) are one group of emerging trace compounds detected in municipal wastewater. Differences in sample storage, preparation, and extraction methods for their measurement have led to variability in results. We analyzed 11 PNMs by GC/MS and compared the results of different storage times and extraction methods (supercritical fluid (SFE) or microwave-assisted (MAE)) for 202 samples of primary sludge, waste activated sludge (WAS), raw sludge, and aerobically/anaerobically digested biosolids collected from Canadian municipal wastewater treatment plants. Sixty-three air-dried samples were extracted by SFE, and 139 air-dried, centrifuged, or filtered samples were extracted by MAE. The mean surrogate recoveries were 89% (standard deviation (SD)=11%) for d(10)-anthracene by SFE and 88% (SD=14%) for d(10)-phenanthrene by MAE. Storage study results showed that PNM concentrations changed by a mean of 7% and 9% for primary sludge and WAS respectively after four weeks and decreased up to 25% after 13.5 months of storage in amber glass containers at -18 degrees C. Air-drying of sludge at room temperature caused losses of about 50% of PNM concentrations compared to centrifugation. The proportions of PNMs present in the liquid phase of sludge samples were less than 5% compared to proportions in the sludge solids. The most complete liquid-solid separation was achieved by filtration of frozen/thawed sludge samples, producing a liquid phase that contained less than 1% of the total musk content of the sample.     

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans from various industrial sources

This study characterized the emissions of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) from the stack flue gases of 17 industrial sources, which were classified into 10 categories. The results show that the mean PCDD/PCDF concentration of secondary zinc smelter (Zn-S) and secondary copper smelter (Cu-S) is 2.44 ng international toxic equivalent (I-TEQ)/Nm3 (N represents normal conditions at 0 degrees C, 760 mmHg), which was found to be significantly greater than that of industrial waste incinerators (mean concentration = 0.15 ng I-TEQ/Nm3). These results imply that the controlling of secondary metallurgical melting processes is more important than industrial waste incineration for the reduction of PCDD/PCDF emissions. The mean emission factors of cement production, Zn-S and Cu-S, are 0.052, 1.99, and 1.73 microg I-TEQ/t product, respectively. For industrial waste incineration, the mean emission factors of waste rubber, waste liquor, waste sludge, industrial waste solid (IWI)-1, IWI-2, IWI-3, and IWI-4 are 0.752, 0.435, 0.760, 6.64, 1.67, 2.38, and 0.094 microg I-TEQ/t feed, respectively. Most of the PCDD/PCDF emission factors established in this study are less than those reported in previous studies, which could be because of the more stringent regulations for PCDD/PCDF emissions in recent years.     

利用污泥进行水体中重金属生物吸附研究现状及展望

对国内外利用废水处理等工业过程中所产生的污泥作为生物吸附剂吸附水体中重金属的研究现状进行了综述和分析，包括其预处理技术、反应机理、主要影响因素、处理效果以及反应器工艺等。同时，对该技术未来的发展趋势进行了展望，指出依托现有废水处理设施进行集约化开发将是该工艺的发展方向。     

Utilization of Dry Calcium Based Flue Gas Desulfurization Waste as a Hazardous Waste Fixation Agent

Several designated hazardous wastes (metal plating waste, oil sludge, heavy metal processing sludge) were studied relative to potential detoxification using dry calcium based FGD sludges. The FGD waste was generated from a pilot scale system which utilized slurried lime, a spray drier, and a bag filter. Following detailed physical and chemical identification of the raw FGD and hazardous wastes, various mixtures were prepared and cured. In all cases, even with the organic sludge, a rigid structural material evolved due to the pozzolanic reactions occurring from the wetted dry FGD waste. Structural characteristics, physical character, and chemical leaching effects were evaluated. The solids were leached via both EPA-RCRA and ASTM proposed leaching procedures. In all cases, the hazardous constituents were retained and not leached. Finally, the feasibility of using dry FGD wastes as fixating materials is discussed.     

The effect of pre-ozonation on the biocompatibility of reactive dye hydrolysates

Pre-ozonation of 14 different reactive dyestuff hydrolysates at alkaline pH was investigated to assess possible relationships between ozone transfer efficiency, first order decolourization kinetics, release of initially complexed heavy metals and relative changes in the biodegradability of the partially oxidized dye waste samples. Biocompatibility of the raw (untreated) and ozonated dye hydrolysates was comparatively tracked through specific oxygen uptake rate measurements from which the respirometric inhibition of biological activated sludge imparted by raw and ozonated reactive dye wastewater with respect to synthetic domestic wastewater was determined. It could be demonstrated that preliminary ozonation of reactive azo dyes increases their biological compatibility more significantly than formazan copper complex, copper complex azo and phythalocyanine dyes as a consequence of heavy metal release associated with the cleavage of associated chromophoric groupings right at the initial stages of pre-ozonation.     

沼渣生物炭基Fenton催化剂的制备及其高效降解吡虫啉农药废水的研究

以废弃物沼渣和含铁剩余污泥为原料,采用一步热解法制备沼渣生物炭基Fenton催化剂(以下简称催化剂),构建了非均相Fenton反应体系处理含吡虫啉模拟废水,考察了H2 O2和催化剂用量对吡虫啉去除率的影响.结果表明,非均相Fenton反应体系中,H2 O2最佳投加量为0.50 g/L,催化剂最佳投加量为1.00 g/L...     

市政污泥水热炭化废水组成成分特征

污泥水热炭化处理被认为是极具潜力的污泥安全处置与资源化利用的技术措施之一。为了解废水中碳、氮、磷、钾和重金属含量随水热炭化反应温度和反应时间的变化规律,对市政污泥190℃和260℃水热炭化不同时间（1、6、12、18和24 h）后的废水组成成分进行了研究。结果表明,水热炭化处理后,废水颜色由黑色变成浅黄色;pH由6.40提高到9.14;TOC、COD和BOD5最高分别增加了13 175 mg/L、55 998 O2mg/L和31 723 O2mg/L;氮和钾含量显著提高,但磷含量降低;Cd、Cr含量由未检测到分别增加到0.060 mg/L和2.326 mg/L,As、Pb含量均由0.032 mg/L分别增加到1.408 mg/L和0.590 mg/L,但Cu、Mn及Zn含量降低。比起反应时间,反应温度对废水组成成分的影响更大。     

Leachates from solid wastes: chemical and eco(geno)toxicological differences between leachates obtained from fresh and stabilized industrial organic sludge

The chemical and ecotoxicological characteristics of fresh and stabilized industrial organic sludge leachates were compared to obtain information regarding how the stabilization process can influence the ecotoxic potential of this industrial waste, which could be used for the amendment of degraded soil. Physicochemical analysis of the sludge leachates, as well as a battery of eco(geno)toxicity tests on bacteria, algae, daphnids, and higher plants (including Vicia faba genotoxicity test) and the determination of hydrolytic enzyme activity, was performed according to standard methods. The chemical comparison of the two types of leachate showed that the samples obtained from stabilized sludge had a lower organic content and higher metal content than leachates of the fresh sludge. The eco(geno)toxicological results obtained with aquatic organisms showed that the stabilized sludge leachate was more toxic than the fresh sludge leachate, both originating from the same industrial organic sludge sample. Nevertheless, phytotoxicity tests carried out with a reference peat soil irrigated with stabilized sludge leachate showed the same toxicity as the fresh sludge leachate. In the case of the industrial solid organic sludge studied, stabilization through a biodegradation process promoted a higher metal mobility/bioavailability/eco(geno)toxicity in the stabilized sludge leachate compared to the fresh sludge leachate.     

一种新型环境矿物材料在废水处理中的应用研究

实验研究表明 ,磷矿石作为一种新型环境矿物材料对重金属离子工业废水具有较好的处理效果 ,且自身具有显著的优点。采用分级处理的方法以及磷矿石的合适用量可以使处理后的工业废水达到排放标准甚至饮用标准 ,同时 ,由于磷矿石去除重金属离子速度快 ,在瞬间即可发生作用 ,使得利用动态法进行工业废水的连续处理成为可能 ,而且不会产生二次污染 ,具有工艺应用意义     

重金属对活性污泥微生物毒性的比较研究

采用发光细菌毒性、活性污泥脱氢酶毒性、硝化抑制毒性3种方法测定Hg、Cd、Zn、Pb 4种重金属对活性污泥微生物的毒性,并对测定结果进行了比较.结果表明,发光细菌毒性测定方法的灵敏度最高,测得的重金属半数有效浓度(ECSO)最低,4种重金属对发光细菌发光强度的抑制程度由大到小顺序依次为Hg>Cd>Zn>Pb;活性污泥脱氢酶毒性和硝化抑制毒性的测定结果与发光细菌毒性测定结果相比,灵敏度相对较低,测得的重金属ECSO相对较高,测得的活性污泥脱氢酶活性的抑制程度由大到小顺序依次为Cd>Hg>Zn>Pb,与测得的活性污泥硝化速率抑制程度大小顺序一致.但2者测得的EC50有所差别.为了更准确的判定重金属对活性污泥微生物的毒性影响.至少应取不同的重金属毒性终点指示指标做一组毒性实验,而不能以发光细菌毒性测定结果作为唯一的判定依据,这可能会过分夸大重金属对污水处理工艺的冲击能力,导致污水处理成本无谓增加.     

Partitioning of nutrients and micropollutants along the sludge treatment line: a case study

A 2-year sampling campaign was conducted in three wastewater treatment plants of various sizes in the Rome area to assess the occurrence of nutrients and micropollutants among primary, secondary and digested sludge. The primary purpose was to evaluate the quality of different sludge types and their suitability for agricultural use. Primary sludge was consistently more polluted than secondary in terms of organic micropollutants, whereas heavy metals partitioned equally among the sludge types. In digested sludge, the heavy metal concentrations were always below limit values proposed for agricultural utilisation. In contrast, organic micropollutants concentrated during anaerobic digestion and affected the quality of the digested sludge. Secondary sludge resulted less polluted and richer in nitrogen and phosphorus (up to three times) than primary sludge and is hence more suitable for agricultural use. Separate processing of primary and secondary sludge might therefore be an innovative option for sludge management that could maximise the possibilities of agricultural use of secondary sludge and limit disposal problems only to primary sludge. In fact, primary sludge could be easily treated and disposed of by conventional processes including thickening, anaerobic digestion, centrifugation and incineration, whereas the difficult digestibility of secondary sludge could be improved by disintegration pre-treatment before stabilisation.     

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.     

Electrokinetic enhancement removal of heavy metals from industrial wastewater sludge

An enhanced electrokinetic process for removal of metals (Cr, Cu, Fe, Ni, Pb, Zn) from an industrial wastewater sludge was performed. The electrokinetic experiments were conducted under a constant potential gradient (1.25 V cm(-1)) with processing fluids of tap water (TW), sodium dodecylsulfate (SDS) and citric acid (CA) for 5 days. Results showed that metal removal efficiency of heavy metals for EK-TW, EK-SDS and EK-CA systems are 11.2-60.0%, 37.2-76.5%, and 43.4-78.0%, respectively. A highest metal removal performance was found in EK-CA system. The removal priority of investigated metals from sludge by EK process was found as: Cu > Pb > Ni > Fe > Zn > Cr. The results of sequential extraction analysis revealed that the binding forms of heavy metals with sludge after electrokinetic process were highly depend upon the processing fluid operated. It was found that the binding forms of metals with sludge were changed from the more difficult extraction type (residual and sulfate fractions) to easier extraction types (exchangeable, sorbed, and organic fraction) after treatment by electrokinetic process. Results imply that if a proper treatment technology is followed by this EK process to remove metals more effectively, this treated sludge will be more beneficial for sludge utilization afterwards. Before it was reused, the risk associated with metals of more mobile forms to the environment need to be further investigated. The cost analysis was also evaluated for the investigated electrokinetic systems.