Optimization of digestion methods for sewage sludge using the Plackett-Burman saturated design

The Plackett-Burman saturated factorial design was used to select optimized dissolution conditions for sewage sludge samples. Three different digestion methods were applied: i) microwave oven digestion in a domestic oven with Parr-type reactors; ii) microwave oven digestion with controlled-pressure reactors; iii) pressure bomb reactor heated on a hot plate. The three methods were validated by statistically comparing the metal contents found with the certified ones of the sewage sludge sample (BCR 145R). No significant differences were obtained and the RSD values were lower than 3% in all cases. The metals were determined by flame-AAS. The variables studied were the following: microwave power; digestion time; predigestion; volume of hydrochloric acid; volume of hydrofluoric acid; volume of nitric acid. The operative advantages offered by microwave digestion with controlled-pressure reactors were also considered. Received: 23 July 1997 / Revised: 31 October 1997 / Accepted: 5 November 1997     

Electron beam pretreatment of sewage sludge before anaerobic digestion

The pretreatment of waste-activated sludge (WAS) by electron beam irradiation was studied in order to improve anaerobic sludge digestion. The irradiation dose of the electron beam was varied from 0.5 to 10 kGy. Batch and continuous-flow stirred tank reactors (CFSTRs) were operated to evaluate the effect of the electron beam pretreatment on anaerobic sludge digestion. Approximately 30–52% of the total chemical oxygen demand (COD) content of the WAS was solubilized within 24 h after electron beam irradiation. A large quantity of soluble COD, protein, and carbohydrates leached out from cell ruptures caused by the electron beam irradiation. Volatile fatty acids production from the irradiated sludge was approx 90% higher than that of the unirradiated sludge. The degradation of irradiated sewage sludge was described by two distinct first-order decay rates (k ₁ and k ₂). Most initial decay reaction accelerated within 10 d, with an average k ₁ of 0.06/d for sewage sludge irradiated at all dosages. The mean values for the long-term batch first-order decay coefficient (k ₂) were 0.025/d for irradiated sewage sludge and 0.007/d for unirradiated sludge. Volatile solids removal efficiency of the control reactor fed with unirradiated sewage sludge at a hydraulic retention time (HRT) of 20 d was almost the same as that of the CFSTRs fed with irradiated sludge at an HRT of 10 d. Therefore, disintegration of sewage sludge cells using electron beam pretreatment could reduce the reactor solid retention time by half.     

Application of thermal analysis for evaluating the digestion of microwave pre-treated sewage sludge

The effect of microwave pre-treatment (MwP) on anaerobic digestion of sewage sludge was studied by means of thermal analysis and evolved gas analysis. The effect of the pre-treatment at low energy input (<1000 kJ L^?1) on sludge solubilisation was studied with the aid of response surface methodology. The pre-treatment process was subsequently studied at energies of 488–2700 kJ L^?1 to evaluate the improvement in biogas production under mesophilic conditions. Organic matter modifications were studied using a Setaram TGA92 analyser at atmospheric pressure coupled to an MSC200 quadrupole mass spectrometer from Balzers. Particle size analysis was carried out using a Laser Diffraction Particle Size Analyser LS 13 320 Beckmann Coulter for evaluating the effect of MwP on sludge particles. Results showed an increase in organic matter solubilisation with the increase in the energy applied. Modifications in the specific surface area of the organic matter due to the MwP resulted in increments in methane yields. However, an accumulation of complex compounds was observed in thermal profiles at the maximum energy input (2700 kJ L^?1). Semi-continuous digestion experiments were evaluated using as substrate pre-treated sludge at the optimum energy value (975 kJ L^?1). Results showed a significant increase in methane yield (43 %) when evaluating the process at hydraulic retention times (HRTs) of 25–10 days.     

Change of thermal drying characteristics for dewatered sewage sludge based on anaerobic digestion

The moisture distribution and thermal drying characteristics of dewatered sludge in anaerobic digestion were investigated by a thermo-gravimetric analyzer (TG) and the isothermal kinetic characteristics during the drying were developed by an unreacted core model. The TG results showed that the bound water was partly converted to the free water with the invariant interstitial water and surface water after anaerobic digestion, which enhanced the drying performance of sludge. The time required for the complete drying of digestate was less than that of the raw sludge in the same temperature. The moisture evaporative efficiency of digestate was related to the vapor diffusion rate of the outer surface, and the drying efficiency of digested sludge cannot be enhanced by increased temperatures.     

Strategy for developing and optimizing liquid chromatography methods in pharmaceutical development using computer-assisted screening and Plackett-Burman experimental design

We describe a three-step method development/optimization strategy for HPLC assay/impurity methods for pharmaceuticals, which include multiple-column/mobile phase screening using a system equipped with a column-switching device, further optimization of separation by using multiple organic modifiers in the mobile phase, and multiple-factor method optimization using Plackett-Burman experimental designs. In the first two steps, commercially available chromatography optimization software, DryLab, was used to perform computer simulations. This allows the method developer to evaluate each condition (one column/mobile phase combination) with retention data from two scouting gradient runs. This approach significantly reduces the number of runs in method development. After a satisfactory separation was obtained, we used a method optimization step with Plackett-Burman experimental designs. The purpose of the 16-injection set experiments was to evaluate nine method factors with regard to method precision, accuracy, sensitivity and specificity. The results provided logical justifications in selecting method parameters such as column temperature, detection wavelength, injection volume, and sample solvent, etc. In data analysis, instead of the traditional mathematical manipulations, we used the graphical methods to examine and present data by creating the so-called main effect plots. Because replicates of design points were not run, the data did not allow the testing of statistical significance. However, it provided visual presentations in a way that is easy to understand for the method developer and end user alike.     

Plackett-Burman experimental design in chiral analysis using capillary electrophoresis

Chromatographia - Plackett-Burman experimental design has been studied in the chiral separation of clenbuterol using capillary electrophoresis (CE). This saturated fractional design approach was...     

Chlorobiphenyls in sewage sludge; comparison of extraction methods

Six extraction methods for the analysis of PCBs (CB-28, CB-52, CB-101, CB-118, CB-138, CB-153 and CB-180) in sewage sludge were tested. A certified reference material (CRM 392) was used for the evaluation of the performance of the methods. Soxhlet-Dean-Starch with toluene as solvent, Soxhlet with hexane:acetone (2:3), cold digestion/saponification with 2 mol/L KOH in methanol followed by partition with hexane, and sonicated liquid-solid extraction with hexane:acetone (1:1) produced accurate results (97%, 93%, 104%, and 88%, respectively) with acceptable precisions (6.2%, 6.8%, 15% and 12%, respectively). Results in close agreement with the certified value for all congeners were obtained by treatment with BF₃-methanol prior to partition with dichloromethane. However, this is a tedious procedure and involves the use of hazardous compounds. Cyclic steam distillation produced results with an accuracy of around 80% and a good precision (5.2%). The very low consumption of solvents and other expensive chemicals by this technique and the possibility of analyzing the extract directly without clean-up make it an interesting alternative to the more sophisticated methods. Column elution with dichloromethane was found to be less efficient (61%), but it is a rapid, direct method with a low consumption of solvents and it may therefore serve as screening method. Received: 29 April 1997 / Revised: 30 July 1997 / Accepted: 6 August 1997     

Chlorobiphenyls in sewage sludge; comparison of extraction methods

Six extraction methods for the analysis of PCBs (CB-28, CB-52, CB-101, CB-118, CB-138, CB-153 and CB-180) in sewage sludge were tested. A certified reference material (CRM 392) was used for the evaluation of the performance of the methods. Soxhlet-Dean-Starch with toluene as solvent, Soxhlet with hexane:acetone (2:3), cold digestion/saponification with 2 mol/L KOH in methanol followed by partition with hexane, and sonicated liquid-solid extraction with hexane:acetone (1:1) produced accurate results (97%, 93%, 104%, and 88%, respectively) with acceptable precisions (6.2%, 6.8%, 15% and 12%, respectively). Results in close agreement with the certified value for all congeners were obtained by treatment with BF₃-methanol prior to partition with dichloromethane. However, this is a tedious procedure and involves the use of hazardous compounds. Cyclic steam distillation produced results with an accuracy of around 80% and a good precision (5.2%). The very low consumption of solvents and other expensive chemicals by this technique and the possibility of analyzing the extract directly without clean-up make it an interesting alternative to the more sophisticated methods. Column elution with dichloromethane was found to be less efficient (61%), but it is a rapid, direct method with a low consumption of solvents and it may therefore serve as screening method. Received: 29 April 1997 / Revised: 30 July 1997 / Accepted: 6 August 1997     

Improving the synthesis of a molecularly imprinted sol-gel for serine using a Plackett-Burman design

We have studied the influence of the experimental conditions during synthesis on the properties of molecularly imprinted sol-gels for serine. The influence of hydrophobicity, presence of amino groups, additives, water/ethanol ratio and type of catalyst (basic or acid) were optimized using a Plackett-Burmann design in 12 blocks. Serine was selected as a target molecule for the imprinting process, and each imprinted and non-imprinted material was studied by competitive and non-competitive protocols. The results demonstrate the strong effect of 3-aminopropyltrimethoxysilane on the recognition capabilities of the materials in competitive assays. The mechanisms of interaction appear to be similar in acid-catalysed sol-gels, whereas sol-gels obtained under base catalysis tend to give interactions affecting the competitive experiments only.

Speciation of heavy metals in sewage sludge after mesophilic and thermophilic anaerobic digestion

Two types of sewage sludge anaerobic digestion were carried out: mesophilic and thermophilic. Metal speciation analysis was performed revealing some changes in the chemical form of the metals during the stabilization process of sludge. After both methane fermentation processes, a comparable level of organic matter distribution was obtained (≈ 40 %). The amount of produced methane during thermophilic and mesophilic digestion was 560 mL of CH4 and 580 mL of CH₄ from 1 g of removed organic matter, respectively. Low concentration of heavy metal ions in the liquid phase of sludge was observed. Metal ions precipitated and remained bound throughout the stabilization process. No accumulation of heavy metals in the mobile fractions of sludge (exchangeable and carbonate) was observed for either digestion process. The highest increase of zinc, copper, nickel, cadmium, and chromium concentration was observed in the organic-sulfide fraction, whereas the highest increase of lead was found in the residual fraction.     

Optimization and comparison of two digestion methods for multi-element analysis of certified reference plant materials by ICP-AES. Application of Plackett-Burman and central composite designs

Two open-vessel wet digestion methods using mixtures of (i) HNO₃ and H₂SO₄ (WD I), and (ii) HNO₃, H₂SO₄ and H₂O₂ (WD II) were developed and optimized for determination of a wide range of elements in plant reference materials by inductively coupled plasma atomic emission spectrometry. A Plackett-Burman fractional factorial experimental design with eight experiments for seven variables was used for the evaluation of the effects of several digestion variables at once. From these studies, certain variables showed up as significant, and they were further optimized by using a star-type central composite experimental design, which involved fourteen experiments. Instrumental variables such as radio-frequency incident power, nebulizer argon gas flow rate and sample uptake flow rate were also optimized. The analytical performance was assessed statistically. Nine elements in total can be simultaneously determined at the concentration levels usually found in plant materials. The agreement between measured and certified values with respect to NIST-SRM 1568a (rice flour), IAEA-331 (spinach leaves) and IAEA-359 (cabbage) proved that the developed methods are well suited for routine elemental analysis of plants or foods of plant origin. Correspondence: George A. Zachariadis, Laboratory of Analytical Chemistry, Department of Chemistry, Aristotle University, GR-54124 Thessaloniki, Greece     

Anaerobic digestion of municipal solid waste and sewage sludge under mesophilic and thermophilic conditions

In this study, thermal analysis in differential scanning calorimetry associated to Fourier self-deconvolution (FSD) of infrared spectra was applied to the study of anaerobic digestion of the organic fraction of domestic solid waste and sewage sludge mixed in 1:1 ratio under mesophilic and thermophilic conditions. Curves showed an exothermic peak in the high-temperature range and a number of endothermic and/or exothermic peaks in the low- and medium-temperature range. The high-temperature exotherm was a common feature on curves of all samples. Digestates evidenced a shift of this exotherm toward higher temperature with respect to both substrates and feed-in materials as a result of a greater chemical complexity attained by organic matter (OM) during the process. A further shift toward higher temperature values was observed on digestates obtained under thermophilic conditions with respect to digestates obtained under mesophilic conditions. This result was associated to a higher recalcitrance of digestates produced under more drastic conditions. Based on evidence obtained by FSD spectra, the exotherm in the medium-temperature range was assigned to combustion of carbohydrates and to loss of aliphatic structures and carboxylic groups. Enthalpy data associated to the high-temperature exotherm were used to differentiate feed-in materials and their corresponding digestates and to distinguish digestates obtained under different operative conditions.     

Optimization of biosurfactant lipopeptide production from Bacillus subtilis S499 by Plackett-Burman design

Bacillus subtilis S499 is well-known for its ability to produce two families of surfactant lipopeptides: Iturin A and Surfactin S1. Fermentation optimization for this strain was performed to amplify the surfactant production. Ten active variables were analyzed by two successive Plackett-Burman designs, consisting respectively of 12 and 16 experiments to give an optimized medium. The amount of biosurfactant lipopeptides in the supernatant of a culture carried out in this optimized medium was about five times higher than that obtained in nonoptimized rich medium. The analysis of the surfactant molecules produced in such optimized conditions has revealed the presence of a third family of lipopeptides: the fengycins. The time-dependent production of these three families of molecules in bioreactors showed that surfactin S1 is produced during the exponential phase and iturin A and fengycins during the stationary phase.     

不同消解方法分析污泥中重金属含量的比较

采用三种电热板消解体系和两种微波消解体系分别对两种类型的污泥进行消解,并以电感耦合等离子体发射光谱法测定其中的Cu、Pb、Cr、Cd、Ni、Zn等11种金属的含量.结果表明,H2O2-王水-HF微波消解体系可实现污泥中重金属的充分溶解,对样品中Cu、Pb、Cr、Ni回收率可达96%~104%,相对标准偏差为0.16%~3.48%.该方法具有精密度好、准确度高、耗酸量少、操作安全简便等优点,适用于污泥中重金属的分析测定.     

Comparison of two extraction methods for the analysis of per- and polyfluorinated chemicals in digested sewage sludge

A rapid and reliable analytical method, based on ion-pair extraction, clean-up on Envicarb cartridge and detection by liquid chromatography–tandem mass spectrometry (LC–MS/MS), was developed for determination of 17 per- and polyfluorinated chemicals (PFCs) in digested sewage sludge. Envicarb cartridge and six labeled internal standards were selected for the elimination/reduction and correction of matrix effects, respectively. As a result, the matrix effect for perfluorooctane sulfonamides (FOSAs) and perfluorocarboxylic acids (PFCAs) with carbon chain length from C6 to C14 was lowered to a range of −14% to +28%. However, the matrix effect for other analytes was still great mainly due to the absence of appropriate internal standard. Mean recoveries of the target analytes based on matrix spikes, at different spike levels (10–300 ng/g), ranged from 70% to 169%. Relative standard deviations (RSDs) were in the range of 2–20% at different spike levels. The limit of quantification (LOQ) ranged between 0.6 and 30 ng/g. The method was successfully applied to several sewage sludge samples from wastewater treatment plants nearby Zürich, Switzerland. In addition, by comparing the accuracy and precision of ion-pair extraction method and methanol extraction method, we further demonstrated that the ion-pair extraction method can be used for the analysis of PFCs in sludge samples. To our knowledge, this is the first study to extract the PFCs in sewage sludge with ion-pair method and to find unsaturated fluorotelomer carboxylic acids (FTUCAs) in sewage sludge.     

Sampling of tar from sewage sludge gasification using solid phase adsorption

Sewage sludge is a residue from wastewater treatment plants which is considered to be harmful to the environment and all living organisms. Gasification technology is a potential source of renewable energy that converts the sewage sludge into gases that can be used to generate energy or as raw material in chemical synthesis processes. But tar produced during gasification is one of the problems for the implementation of the gasification technology. Tar can condense on pipes and filters and may cause blockage and corrosion in the engines and turbines. Consequently, to minimize tar content in syngas, the ability to quantify tar levels in process streams is essential. The aim of this work was to develop an accurate tar sampling and analysis methodology using solid phase adsorption (SPA) in order to apply it to tar sampling from sewage sludge gasification gases. Four types of commercial SPA cartridges have been tested to determine the most suitable one for the sampling of individual tar compounds in such streams. Afterwards, the capacity, breakthrough volume and sample stability of the Supelclean? ENVI-Carb/NH₂, which is identified as the most suitable, have been determined. Basically, no significant influences from water, H₂S or NH₃ were detected. The cartridge was used in sampling real samples, and comparable results were obtained with the present and traditional methods.     

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.     

Statistical mixture design development of digestion methods for Oyster tissue using inductively coupled plasma optical emission spectrometry for the determination of metallic ions

The quantitative determination of chemical elements in organic or biological samples is an important analytical problem. Normally the elements to be determined in the organic matrix must be transformed into a simple inorganic form. A digestion method by heating on a block digestor has been developed for the determination of Al, As, Ba, Ca, Cd, Co, Cu, Fe, Mg, Mn, V and Zn in Oyster tissue by ICP OES. A simplex centroid statistical mixture design has been used to study the effects of changing HNO₃, HCl and H₂O₂ reagent proportions on the digestion of these samples. Response surface and principal component analyses show that the species Ca, Cd, Cu, Fe, Mg, Mn and Zn have very similar analytical tendencies under this experiment. By means of mixture modeling maximum recoveries for these ions were predicted using 19%, 18% and 63% of the HCl, HNO₃ and H₂O₂ pseudocomponent mixtures, respectively. This corresponds to 21.4%, 30.8% and 47.8% of the HCl, HNO₃ and H₂O₂ commercial solutions. Furthermore the As, Co and V ions present large recoveries for these mixtures as well. The Al and Ba ion recoveries are seen to be independent of the mixture proportions. The analysis of Oyster tissue reference material (SRM 1566b - NIST) under optimized conditions at the selected wavelengths resulted in ion recoveries between 90% and 100%.     

Slow pyrolysis of pre-dried sewage sludge

This study focuses on the use of slow pyrolysis with controlled temperature increase for the thermal decomposition of pre-dried wastewater sludge. A combination of two significantly different methods was applied to investigate the pyrolysis process. The first of the experimental approaches was based on laboratory apparatus with a vertical batch retort equipped with external electrical heating. Samples of the liquid and gaseous products of the pyrolysis were taken at defined intervals throughout the pyrolysis process and were subsequently analysed. The second method involved the application of thermal analysis to the identical sludge, completed by online analysis of the pyrolysis products generated. This second method included thermogravimetry (TG), differential thermal analysis (DTA), and differential scanning calorimetry (DSC). The results obtained by both methods demonstrate that waste water sludge can be effectively converted into pyrolysis gas and oil with good combustion properties.