Thermal behavior of residues (sludge) originating from the sugarcane industry

The Brazilian sugarcane industry shows a great amount of generated sludge which should be utilized adequately. Two sludge samples, aerobic and anaerobic, were collected. Both were evaluated by thermogravimetry and differential thermal analysis (DTA) as well as X-ray power diffraction. These compounds show variations of mass between 30 and 140 °C due to the dehydration stage. The DTA curves show that the compounds have an exothermic reaction between 450 and 550 °C, which indicates that this can be used as an energy source. Details concerning the kinetic parameters of the dehydration and thermal decomposition have also been described here. The kinetic study of these stages was evaluated in open crucibles under nitrogen atmosphere. The obtained data were evaluated with the isoconversional kinetic method. The results show that different activation energies were obtained for thermal decomposition.     

Application of thermo-electrochemistry to simultaneous leaching of sphalerite and MnO2

In order to enhance the electrogenerative leaching rate of sphalerite reasonably, the basic principle of generative process was applied to the simultaneous leaching of sphalerite in the presence of MnO₂. It was confirmed by experimental results that both mental ions and electric energy could be obtained in the simultaneous electrogenerative leaching process. The leaching cell had the open circuit potential about 1.0 V, about 2000 C of electric quantity was obtained, the optimal leaching ratio of Zn²⁺ and Mn²⁺ was 48.5, 39.6% respectively, after electrogenerative leaching for 11 h.     

Thermal analysis of soil amended with sewage sludge and biochar from sewage sludge pyrolysis

The main objective of the present study is to study the behaviour of sewage sludge and biochar from sewage sludge pyrolysis after addition to soil in a context of a temperate agricultural soil. For this, an incubation experiment was designed during 200 days. Carbon mineralization of soil amended with sewage sludge and biochar at two different rates (4 and 8 wt%) was evaluated. Differential thermal analysis, thermogravimetry and the first derivate of the TG were performed in oxidizing conditions on soil samples before and after incubation. Biochar obtained from sewage sludge pyrolysis at 500 °C was more stable in soil than original sewage sludge. After incubation experiment, the reduction of soil organic matter content was significantly lower in soil amended with biochar than in soil amended with sewage sludge. The thermostability index WL₃/WL₂ decreases after incubation in soil amended with biochar, however it increases in case of soil treated with sewage sludge.     

城市污水污泥燃烧特性和动力学特性分析

采用热重分析仪对城市污水污泥进行热重实验,通过TG(热重)、DTG(微分热重)和DSC(差示扫描量热)曲线的分析对比,获得污水污泥热解和燃烧不同阶段的特性。低于250℃,燃烧与热解的热重曲线基本吻合,说明在此之前,失重速率主要受控于有机物的分解以及析出,燃烧过程对失重影响不明显。燃烧DTG曲线呈现“W”峰型,第一个失重速率峰与热解DTG曲线基本对应,高于410℃,燃烧DTG曲线出现显著的加速。采用Coats-Redfern 积分法,假设不同的反应模型进行拟合,推断出污泥燃烧过程中两个DTG峰体现出不同的反应机理。借鉴煤燃烧机理分析认为,污泥燃烧反应初期挥发分的燃烧受控于化学反应速率,随着温度的不断提高,剩余挥发分的燃尽和固定碳的燃烧总反应速率逐渐受扩散因素控制。基于分析所得污泥燃烧机理,采用四个独立的平行反应模型模拟污泥的燃烧过程,拟合曲线与实验数据吻合良好。     

Thermal analysis of growing media obtained from mixtures of paper mill waste materials and sewage sludge

This study deals with thermal analysis of growing media obtained from mixtures of paper will waste materials (one de-inking paper sludge, HP, and one reject from paper mill producing paper from virgin wood, RT) with sewage sludge. For the growing media formulation, one sewage sludge (L) was mixed with both paper mill waste materials at 10, 20, and 30% in volume. An incubation experiment was designed in order to study their carbon mineralization. Addition of sewage sludge significantly increases the carbon mineralization of growing media based on RT. In case of HP, carbon mineralization increases after addition of sewage sludge in 30% (HP + 30L treatment). Thermogravimetric analysis (TG and DTG) of growing media was performed before and after incubation experiment in order to study the organic matter transformation. The higher the carbon mineralization, the greater the difference between TG curves of samples before and after the incubation. The WL₃/WL₂ ratio increases after incubation of samples as a result of organic matter stabilisation. For HP growing media, the highest value corresponds to HP + 30L whereas HP + 20L, and HP + 10L show similar values. In case of RT, the WL₃/WL₂ index shows a progressive increase with sewage sludge content.     

Effect of sludge pH and treatment time on the electrokinetic removal of aluminum from water potabilization treatment sludge

Algerian's municipal sewage treatment plants generate around 10⁶ m³ of sewage sludge annually. Recently, rapid expansion of wastewater treatment plants without equal attention to the treatment of the produced sludge has generated increasing concerns. While the sludge is usually incinerated or used as an agricultural fertilizer and may contain numerous nutrients, there may also be harmful substances that complicate sludge management. Hence the removal of pollutants from the sludge is necessary before further usage. This paper discusses the characteristics of potable water treatment sludge containing a high aluminum content. Furthermore, an electrokinetic treatment is proposed to remove aluminum from this sludge by varying the type of solution contained in the cathode compartment and modifying the treatment time to optimize the efficiency of the process. Successful results were achieved where 60% of aluminum was collected on the cathode side with a consumed energy around of 1000–2000 kWh kg⁻¹ of sludge weight.     

Thermal decomposition study of sewage sludge and of organicwaste used in the sorption of metals

The conventional treatments of effluents containing heavy metals produce significant quantities of byproducts with recalcitrant characteristics, making necessary looking after alternative techniques in order to avoid the production of new contaminated residues. Sorption process of chromium and zinc in vertical columns loaded with sewage sludge and organic solid waste has been studied in this work. The data from the TG curves of the two sorbents presented significant differences when they were submitted to the metal uptake, being noticed the displacement of the thermal events towards lower temperatures for both types of sorbents studied. As it was expected, for both sorbents, an increase in the mass of samples has been observed at the completion of the thermal tests upon metal uptake. Therefore, these facts demonstrate that during the biosorption process a physico-chemical interaction took place between sorbents and metals, as it was evidenced by the more than 100 K increase in the decomposition temperatures as well as the variation of the ΔH values of the samples.     

Microwave-assisted extraction (MAE) for the determination of polybrominated diphenylethers (PBDEs) in sewage sludge

An efficient microwave-assisted extraction (MAE) method has been developed and evaluated for the quantification of eight major polybrominated diphenylethers (PBDEs) in sewage sludge. The PBDEs were extracted from wet and dry sludge in a microwave extraction unit using a hexane/acetone mixture for 35 min at a controlled temperature of 130 °C. The extract was concentrated, cleaned up on a silica gel column, and analyzed by gas chromatography/mass spectrometry (GC/MS) in the negative chemical ionization (NCI) mode. The MAE procedure exhibited higher extraction efficiency, specifically for BDE (brominated diphenylether) 209, than the conventional Soxhlet extraction. The test congeners were clearly separated under specific instrumental operating conditions, at a source temperature of 230 °C and a column length of 20 m. The present analytical method showed recovery efficiencies ranging from 80 to 110% when applied to the PBDE-free sludge spiked with eight PBDE congeners. The efficiency of the MAE method was confirmed using sludge obtained from four sewage treatment plants (STPs). The results indicate that BDE 47, 99, and 209 are the most abundant congeners present in these sewage sludges, which is consistent with previous reports.     

Study of the complexation of Cu(II) by fulvic acids extracted from a sewage sludge and its compost

 The complexation of Cu(II) by two samples of fulvic acids (FA) extracted from the raw sewage sludge (RsFA) of a waste water processing plant and from the composted sludge (CsFA) obtained upon aerobical digestion was studied at pH 6.0. Synchronous molecular fluorescence spectroscopy was used to monitor the association of FA with Cu(II) and a self-modelling mixture analysis method (SIMPLISMA) was used to preprocess the spectral data to calculate the number of components with different quenching profiles as function of the Cu(II) concentration and their spectra. The stability constants and a rough estimation of the binding site concentrations were obtained by a Stern-Volmer analysis, by a non-linear least-square method and by a linear procedure. The analysis of the SyF spectra allowed the identification of two binding sites for both samples. The logarithm of the conditional stability constant corresponding to the 1:1 complex formed between the stronger binding site and Cu(II) is about 4 for both samples. Received: 22 April 1996 / Revised: 5 August 1996 / Accepted: 7 August 1996     

Determination of azoles in sewage sludge from Spanish wastewater treatment plants by liquid chromatography-tandem mass spectrometry

A simple and rapid analytical method for the determination of 16 azoles in sewage sludge has been developed and validated. The method was based on ultrasound-assisted extraction followed by dispersive solid-phase extraction cleanup and liquid chromatography-electrospray tandem mass spectrometric detection. The azoles were selected by their intensive usage as biocides (tebuconazole, propiconazole, cyproconazole and thiabendazole), antimycotic pharmaceuticals (ketoconazole, econazole, fluconazole and clotrimazole) or fungicides in agriculture (difenoconazole, flusilazole, hexaconazole, prochloraz, bromuconazole, epoxiconazole and triticonazole). The recoveries of these compounds through the method were between 71.9 and 115.8%, with relative standard deviations lower than 20%. Detection limits were in the range of 0.5-5.0 ng/g. The developed method was applied to the analysis of azoles in sewage sludge samples collected from 19 Spanish wastewater treatment plants. Although azoles used as biocides or agriculture fungicides were present in a few sludge samples, the pharmaceuticals ketoconazole, econazole and clotrimazole were present in all of the analyzed sludge samples, being ketoconazole the one found at the highest level, representing the 68.6% of the total azole content found in the 19 sludge samples studied.     

Recovery and stabilization of heavy metal sludge (Cu and Ni) from etching and electroplating plants by electrolysis and sintering

This work dealt with the recovery and stabilization of the sludge with heavy metals (Cu and Ni) produced from etching and electroplating plants. The heavy metals in the sludge were deprived of by acid leaching, followed by precipitation with 28% NH₄OH, and finally by electrolysis. In the electrolysis, the recovery percentage and purity were investigated at different electronic currency and temperature. The metal-deprived sludge was stabilized by mixing with glass powder and clay, followed by sintering at high temperature. How the ratio of glass powder to metal-deprived sludge affected final products (sludge bricks) was explored, in terms of specific gravity, absorption capacity, unconfined compressive strength, morphology, the volume shrinkage ratio and burn-up ratio. The volume shrinkage ratio and burn-up ratio of sludge bricks increased with metal-deprived sludge contents. The heavy metal remaining in sludge bricks was assessed through TCLP (toxicity characteristic leaching procedure) and by the analysis of SEM and EDX. The results from TCLP showed that the contents of leached metals were all below the regulatory criteria. This fact approved the feasibility of our method.     

Thermal behavior of polyacrylonitrile and poly(vinylpyrrolidone-graft-acrylonitrile) blend

The role of hydrophilic poly(vinylpyrrolidone-graft-acrylonitrile) (PGA) copolymer and the plasticization effect of water in melting behavior of polyacrylonitrile (PAN)-PGA blend were investigated. The PAN-rich PGA blend was obtained by in situ polymerization of the PAN homopolymer and the PGA copolymer. Depression of the melting point of PAN in the presence of the PGA occurred, thereby involving an endothermic transition of the wet blend powder at atmospheric pressure. This was due to a plasticization effect of water inducted into PAN matrix by the PGA. X-ray scattering showed that in the blend powder the crystalline phase of PAN was unaffected by PGA and the amorphous phase of PAN contained PGA domain. On compressing with heating, the wet blend powder formed a transparent sheet, in which the crystalline structure of PAN was changed from hexagonal to orthorhombic lattice. The amount of PAN chain participating in thermal motion for melting varies with absorbed water content. © 1996 John Wiley & Sons, Inc.     

Thermal behavior and water adsorption of natural and modified sepiolite having dolomite from Turkey

The water adsorption properties of sepiolite having dolomite supplied from Eskisehir region and their exchanged forms (K⁺, Na⁺, Mg²⁺ and Ca²⁺) were investigated. The sepiolite samples were characterized using XRD, TG-DTA, DSC and nitrogen adsorption methods. The temperature ranges were determined for the dehydrations of hydroscopic and zeolitic water as 30–200°C, for the dehydration of the bound water as 250–750°C and for the dehydroxylation of hydroxyls as 810–850°C in the sample. It was observed that the value of percent mass loss for natural and modified samples varied in the range from 36.70 to 39.05%. Two mass loss steps for all samples were observed using a differential scanning calorimetry (DSC) in the range of 30–550°C. Adsorption isotherms for water on natural and modified forms were obtained at pressures up to 2.39 kPa. Uptake of water increased as K-SEP.<Na-SEP.<Mg-SEP.<Ca-SEP. for sepiolite samples at 293 K.     

Novel analytical procedures for screening of drug residues in water, waste water, sediment and sludge

Traces of pharmaceuticals are continuously introduced into the aquatic environment mainly by sewage treatment plant effluents. Final data about their impact on the ecosystem are still partly missing. Progress in instrumental analytical chemistry has resulted in the availability of methods that allow a monitoring of these pollutants at ng L⁻¹ levels. In this review the state-of-the-art of residue analysis of pharmaceuticals by chromatographic and electrophoretic techniques is summarized. Improvements in detection limits over the past years have mainly been due to sophisticated mass spectrometric detection techniques. Furthermore, robust sample preparation and preconcentration protocols based on solid-phase extraction and related procedures have contributed significantly to the achievements observed so far. This review also covers several immunochemical approaches which may serve as an inexpensive alternative for quick screening of samples.     

Thermal behavior of copper(II) 4-nitroimidazolate

The thermal behavior of copper(II) 4-nitroimidazolate (CuNI) under static and dynamic states are studied by means of high-pressure DSC (PDSC) and TG with the different heating rates and the combination technique of in situ thermolysis cell with rapid-scan Fourier transform infrared spectroscopy (thermolysis/RSFTIR). The results show that the apparent activation energy and pre-exponential factor of the major exothermic decomposition reaction of CuNI obtained by Kissinger’s method are 233.2 kJ mol⁻¹ and 10^17.95 s⁻¹, respectively. The critical temperature of the thermal explosion and the adiabatic time-to-explosion of CuNI are 601.97 K and 4.4∼4.6 s, respectively. The decomposition of CuNI begins with the split of the C-NO₂ and C-H bonds, and the decomposition process of CuNI under dynamic states occurs less readily than those under static states because the dynamic nitrogen removes the strong oxidative decomposition product (NO₂). The above-mentioned information on thermal behavior is quite useful for analyzing and evaluating the stability and thermal charge rule of CuNI.     

Alterations in the fat body cells of Rhinocricus padbergi (Diplopoda) resulting from exposure to substrate containing sewage sludge

The final disposal of residues generated at sewage treatment plants (STPs) has become a major problem for cities, due to the increase in the amount of treated sewage. One of the alternatives for the residue, labeled "sewage sludge," is its reuse in agriculture and in degraded soil. However, not all pathogens and metals present in it are eliminated during treatment. Diplopods have been used as bioindicators in ecotoxicological tests as they are constantly in close contact with the soil. Owing to this fact, the purpose of this study was to expose specimens of the diplopod Rhinocricus padbergi to substrate containing sewage sludge collected at STPs to analyze morphological alterations in their parietal and perivisceral fat body, where substances are stored. The exposures were held for 7, 15, or 90 days at different concentrations of sewage sludge (control, 1%, 10%, and 50%). The parietal fat body showed no alterations in any of the three exposure periods or concentrations. Alterations in the perivisceral fat body were observed for all exposure periods. According to the results, we suggest that the sludge used has toxic agents responsible for changing the animal's perivisceral fat body.     

Fe3O4-modified sewage sludge biochar for U(VI) removal from aqueous solution: performance and mechanism

Journal of Radioanalytical and Nuclear Chemistry - Sewage sludge-derived biochar (SSB) was prepared at 600&nbsp;°C pyrolysis temperature and modified by co-precipitation with Fe3O4 to...     

Indirect spectrofluorimetric determination of arsenic at nanotrace levels in alloys, underground water, industrial waters and sewage sludge

An inexpensive and virtually specific nonextractive Spectrofluorimetric method for the determination of As(III) (1 ng/ml-1 g/ml) in 0.18–1.08N H₂SO₄ has been developed. A known excess of Cr(VI) is allowed to quantitatively oxidize As(III) in the essential presence of a mixture of iodide and chloride as catalyst, followed by the addition of excess 2-(-pyridyl) thioquinaldinamide and measurement of the fluorescence intensity (_em(max) = 488 nm _ex(max) = 360 nm) caused by Cr(VI) remaining after As(III) oxidation. The measurement is repeated without As(III) addition and the decrease in fluorescence intensity gives the As(III) concentration with the help of a calibration graph. The method is very precise and accurate (S. D. = ± 0.474, R. S. D. = 0.95%, for the analysis of 50ng/ml As(III), 11 replicates). The detection limit is 0.3ng/ml As(III). Large excesses of over fifty cations, anions and some complexing agents do not interfere. The method has been successfully applied for arsenic determination in various complex matrices: environmental waters, sewage sludges and several certified reference materials (alloys). This method has also been extended to determine As(V), after its reduction to As(III), in water samples, waste discharge water and sewage sludges.Presented at International Conference Arsenic in Ground Water: Cause, Effect and Remedy, Calcutta, India, February, 1995     

Thermal behavior of coffee oil (Robusta and Arabica species)

Coffee seeds are a source for obtaining oil which is used in the candy, soluble coffee, and cosmetics industries. The main purpose of this study was the investigation of the lipid profile and thermal behavior of the roasted and in nature coffee oil of Arabica and Robusta species, using thermogravimetry, differential thermal analysis, derivative thermogravimetry, differential scanning calorimetry (DSC), and modulated DSC. Details concerning the thermal decomposition as well as data of the kinetic parameters have been described here. The kinetic studies were evaluated from several heating rates with a sample mass of 10 mg in open crucible under nitrogen atmospheres. The obtained data were evaluated with the isoconversional kinetic method, where the values of activation energy (E _a/kJ mol^?1) were evaluated in function of the conversion degree (α). In addition, this oil was evaluated by modulated DSC from 25 to ?60 °C, where the transition phase behavior was verified.     

液相色谱-串联质谱法测定污水处理厂水样中双酚A、四溴双酚A及烷基酚类化合物

近年来,双酚A、四溴双酚A及烷基酚类化合物由于其对水生生物的内分泌干扰作用受到越来越广泛的关注。污水处理厂是处理这类化合物的重要途径,研究目标物在其中的浓度分布对于探明此类物质在环境中的暴露水平具有重要意义,而建立相应的分析测定方法则是开展上述研究的基础。本研究建立了同时测定污水处理厂水样中双酚A、四溴双酚A及6种烷基酚类化合物的反相液相色谱-电喷雾串联质谱分析方法。结果发现,以ZORBAX Eclipse Plus C18色谱柱（150 mm×2.1 mm,3.5 μm）为分离柱,乙腈和0.02%（v/v）氨水溶液为梯度洗脱的流动相,电喷雾质谱负离子模式下目标化合物在11 min内分离;在1~100 μg/L范围内,双酚A、四溴双酚A及6种烷基酚类化合物的峰面积与质量浓度的线性关系良好（R²≥0.998）,方法定量限为2.0~20 ng/L;添加水平分别为0.2、2、20 μg/L时,目标化合物的平均回收率分别为64.3%~118.0%、65.9%~100.5%、70.3%~102.7%,相对标准偏差均小于7.1%。基于上述方法,对江苏省某工业园区污水处理厂水样中相关物质进行检测,出水中检出5种目标化合物,质量浓度范围为11.9~3015.3 ng/L。结果表明,该方法准确可靠、灵敏度高,适用于污水处理厂水样中相关烷基酚类化合物的检测。