Three-way multivariate analysis of metal fractionation results from sediment samples obtained by different sequential extraction procedures and ICP-OES

Three typical schemes for metal fractionation were applied to analyse coastal surface sediment samples from Bahía Blanca estuary, where an important industrial emplacement is located. Also, three certified reference materials for total metal concentrations were analysed. The studied metals were cadmium, chromium, copper, lead and zinc because of their hazardous potential and related abundance in the estuary. The concentration of metals was determined by inductively coupled plasma-optical emission spectrometry (ICP-OES). A three-way multivariate analysis was performed in order to obtain a better visualization of the experimental data. The extracted information was used to evaluate the equivalence among the results obtained by the three sequential extraction schemes. The data were analysed by parallel factor analysis (PARAFAC). PARAFAC models with two factors describe appropriately the data sets (explained variance about 54% and core consistency of 100%). The multivariate decomposition showed that the three applied schemes are able to describe equally well the behaviour of the metals in the different sediment fractions.     

Shortened screening method for phosphorus fractionation in sediments: A complementary approach to the standards, measurements and testing harmonised protocol

The SMT protocol, a sediment phosphorus fractionation method harmonised and validated in the frame of the standards, measurements and testing (SMT) programme (European Commission), establishes five fractions of phosphorus according to their extractability. The determination of phosphate extracted is carried out spectrophotometrically. This protocol has been applied to 11 sediments of different origin and characteristics and the phosphorus extracted in each fraction was determined not only by UV-Vis spectrophotometry, but also by inductively coupled plasma-atomic emission spectrometry. The use of these two determination techniques allowed the differentiation between phosphorus that was present in the extracts as soluble reactive phosphorus and as total phosphorus. From the comparison of data obtained with both determination techniques a shortened screening method, for a quick evaluation of the magnitude and importance of the fractions given by the SMT protocol, is proposed and validated using two certified reference materials.     

Semiquantitative determination of residues of amphetamine in sewage sludge samples

A procedure based on HPLC and mass spectrometric detection has been developed for screening of residues of the illicit drug amphetamine in sewage sludge. Sample pretreatment consisted in extraction by 50 mM formic acid and methanol (80:20 v/v), followed by adjustment of the pH to 10 and preconcentration by SPE at poly(di-vinylbenzene)-N-vinylpyrrolidone. HPLC separation of the extract was done on a C18 RP with a mixture of 50 mM formic acid and methanol (80:20 v/v) as mobile phase. The mass spectrometer was operated in the MS2 and MS3 mode using the transition from m/z 136 to 119 and from m/z 119 to 91. Due to the complex matrix, ionization suppression effects as well as shifts in the sensitivity of the detector within a series of runs could not be fully excluded. Therefore, quantitation was done by standard addition together with external standards, so that semiquantitative results could be obtained down to concentrations of 2 microg/kg sewage sludge. Samples taken from various municipal sewage treatment plants indicate that amphetamine residues are ubiquitous in urban areas.     

Determination of perfluorooctanesulfonate and perfluorooctanoic acid in sewage sludge samples using liquid chromatography/quadrupole time-of-flight mass spectrometry

A new method is developed for the determination of perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA) in sewage sludge samples. The analytes in sewage sludge samples are extracted by methanol and formic acid, cleaned by C18 solid-phase extraction, then separated, identified and quantitated by liquid chromatography/quadrupole time-of-flight mass spectrometry (LC–QTOF-MS). A C18 column (150 mm × 2.1 mm, 3.5 μm) with gradient elution of MeOH–H₂O (60:40) containing 5 mmol/L ammonium acetate and MeOH–H₂O (80:20) is used for the chromatographic separation. [M−K]⁻ ions at m/z 498.93 for PFOS and [M−COOH]⁻ ion at m/z 368.97 for PFOA are selected for QTOF-MS in the negative electrospray ionization mode. The detection limits for PFOS and PFOA in sewage sludge samples are 0.5 and 0.8 ng/g, respectively. The spiked recoveries are in the range of 85–114 and 71–98% for PFOS and PFOA, respectively. The proposed method is successfully applied to the analysis of PFOS and PFOA in 16 sewage sludge samples from China. PFOS and PFOA are detected in most sewage sludge samples and the concentrations of PFOS and PFOA are up to 5383 and 4780 ng/g (oven dry weight), respectively.     

Development and validation of a method for analyzing polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in sewage sludge samples

Summary A method has been developed for the analysis of polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) in sewage sludge samples. It was found that PCDD/F are best Soxhlet extracted from the matrix with toluene for 24h, after having tested other solvents (dichloromethane and hexane/acetone 41/59) and other extraction times. Several clean up steps (sulfuric acid, multilayer silica and Florisl columns) and concentration are required prior to analysis of the extract by high resolution gas chromatography-high resolution mass spectrometry (HRGC-HRMS). The complete procedure has been validated and the accuracy and precision data (repeatability and reproducibility) are given. The method is linear in the range studied and the limit of detection ranges between 0.2 and 2.2 pg g⁻¹ of dry matter for the 2,3,7,8-substituted congeners. Moreover, the suitability of the method has been checked in an international interlaboratory comparison. The successful application of this method to several samples from Catalan and Dutch urban wastewater treatment plants was demonstrated.     

Heating process characteristics and kinetics of sewage sludge in different atmospheres

The treatment of wastewater generates a by-product, sewage sludge, the disposal of which poses problems. There are, however, a number of options for making use of this residue, including its conversion into a valuable fuel. The aim of this paper is to describe the process of the heating of sewage sludge under different atmospheres of helium and oxygen and to obtain the kinetic parameters by means of a mathematical model, a heating rate of 10 °C/min being used. Measurements were taken by thermogravimetry and mass spectrometry, and proximate and elementary analyses were made of the sludges and their calorific values were determined. Visual observation of the heating profiles shows four stages in the heating process, which have been characterized. The model proposed was found to adequately describe the weight loss of the sludges studied, while making it possible to obtain the kinetic parameters for the differentiated stages in the thermal process but not to establish any clear tendency of the evolution of these parameters with the increase in oxygen in the heating atmosphere.     

Development of a matrix solid-phase dispersion method for the determination of polycyclic aromatic hydrocarbons in sewage sludge samples

A new, single-step extraction and purification method based on matrix solid-phase dispersion (MSPD) was developed to determine 17 polycyclic aromatic hydrocarbons (PAHs) in sewage sludge samples. The MSPD method consists of sample homogenisation, exhaustive extraction and clean-up by a single process. The different operational parameters of the method, such as the type of dispersant, type and amount of additives, clean-up co-sorbent and extractive solvent were evaluated. Reversed-phase (C18) and polymeric (Oasis HLB and Oasis MAX) materials, as well as normal phase sorbents (Florisil, silica, neutral alumina) and an inert support (sand) were tested to assess the sorbents effect on the yield and selectivity of the MSPD process. Analysis of extracts was performed by high performance liquid chromatography (HPLC) coupled with fluorescence detection.Quantification limits obtained for all of these considered compounds (between 0.0001 and 0.005 μg g⁻¹ dry mass) were well below of the limits recommended in the EU. The extraction yields for the different compounds obtained by MSPD ranged from 76.3% to 103.6%. On the other hand, the extraction efficiency of the optimised method is compared with that achieved by microwave-assisted extraction and the method was applied to the analysis of real sewage sludge samples. A certified reference material (sewage sludge (BCR 088)) and a reference material (sewage sludge (RTC-CNS312-04)) were used to validate the proposed method.     

Combination of gravitational SPLITT fractionation and field-flow fractionation for size-sorting and characterization of sea sediment

A combination of gravitational split-flow thin (SPLITT) fractionation and sedimentation/steric field-flow fractionation (Sd/StFFF) has been used for continuous size-sorting of a sediment sample and for size analysis of the collected fractions. An IAEA (International Atomic Energy Agency) sediment material was separated into four size fractions (with theoretical size ranges <1.0, 1.0–3.0, 3.0–5.0, and >5.0 m in diameter) by means of a three-step gravitational SPLITT fractionation (GSF) for which the same GSF channel was used throughout. The GSF fractions were collected and examined by optical microscopy (OM) and by Sd/St FFF. The mean diameters of the GSF fractions measured by OM were within the size interval predicted by GSF theory, despite the theory assuming that all particles are spherical, which is not true for the sediment particles. The Sd/St FFF results showed that retention shifted toward shorter elution time (or larger size) than expected, probably because of the shape effect. The results from GSF, OM, and Sd/StFFF are discussed in detail.     

Application of a wavelength-dispersive particle-induced X-ray emission system to chemical speciation of phosphorus and sulfur in lake sediment samples

The chemical speciation of phosphorus and sulfur in lake sediment was performed by analyzing Kα X-ray spectra recorded with a high-resolution wavelength-dispersive particle-induced X-ray emission (WD-PIXE) system. The concentrations of phosphorus and sulfur in the sediment were 2500 and 7000 ppm, respectively. To measure both minor elements in a reasonable measurement time, a 2-MeV proton beam with a high current density (6 nA/mm²) was used for the chemical speciation. The possible chemical state change caused by the proton irradiation was studied in order to determine the maximal irradiation time without significant change. We found that the chemical states of phosphorus and sulfur were stable under a beam current density of 6 nA/mm² and a measurement time of 60 min (phosphorus) and 90 min (sulfur). The chemical states of phosphorus and sulfur were determined to be P⁵⁺ and a mixture of S²⁻ and S⁶⁺, respectively.     

Treatment of sewage sludge generated in municipal wastewater treatment plants

This study was designed to evaluate the performance of a cylindrical anaerobic digester in treating secondary sewage sludge. A series of three independent batch experiments was performed for a total operation time of 60 d. The system of anaerobic digestion showed stability conditions, with no noticeable scum or foaming problems. The chemical oxygen demand reduction reached 29, 21, and 45% in sludge and 95, 85, and 82% in supernatant for the three experiments, respectively. Total coliform bacteria levels in the digester ranged from 10⁴ to 10⁵ in influent sludge and from 10⁴ to 10³ in effluent sludge, with an average reduction of 90%. Fecal coliforms of the order of 10⁴ were enumerated in influent sludge and those of the order of 10⁰ were enumerated in effluent sludge, with an average reduction of 99.9%. The studied system had satisfactory results, showing that both organic matter and indicator bacteria levels substantially decrease when the sludge is submitted to anaerobic digestion.     

Field-flow fractionation: Analytical and micropreparative methodology

Since the introduction of the general concept, field-flow fractionation (FFF) was developed to a complex of separation methods that differ by the fundamental processes underlying and accompanying the separation. In this review, the basic principles on which this separation methodology lies are presented, the most important methods and techniques applicable for analytical and preparative fractionations are described, the first approximation theoretical treatment of the separation processes is outlined, and typical applications for analytical and micropreparative purposes are demonstrated. The main goal is to show that FFF represents an interesting and competitive option of the separation methods applicable in analytical chemistry. The existence of some conflicting opinions concerning the theory as well as the experiments does not prohibit the analytical and preparative use of FFF. If not regarded only as a routine analytical tool, it should stimulate the research and development efforts. On the other hand, when used as an analytical tool, even if the approximate theoretical models are not fully supported by the experiments, the correct analytical result can be obtained from FFF (as well as from any other analytical separation method) by using a calibration procedure and an appropriate treatment and interpretation of the raw experimental data.     

Improved sample treatment for the determination of insoluble soap in sewage sludge samples by liquid chromatography with fluorescence detection

A new selective and sensitive method for the determination of insoluble fatty acid salts (soap) in sewage sludge samples is proposed. The method involves a clean up of sample with petroleum ether, the conversion of calcium and magnesium insoluble salts into soluble potassium salts, potassium salts extraction with methanol, and a derivatization procedure previous to the liquid chromatography with fluorescence detection (LC-FLD) analysis. Three different extraction techniques (Soxhlet, microwave-assisted extraction and ultrasounds) were compared and microwave-assisted extraction (MAE) was selected as appropriate for our purpose. This allowed to reduce the extraction time and solvent waste (50 mL of methanol in contrast with 250 mL for Soxhlet procedure). The absence of matrix effect was demonstrated with two standards (C_13:0 and C_17:0) that are not commercials and neither of them has been detected in sewage sludge samples. Therefore, it was possible to evaluate the matrix effect since both standards have similar environmental behaviour (adsorption and precipitation) to commercial soaps (C_10:0-C_18:0). The method was successfully applied to samples from different sources and consequently, with different composition.     

Extraction and determination of sulfonamides, macrolides, and trimethoprim in sewage sludge

Pressurized liquid extraction (PLE) was optimized and validated for the determination of sulfonamide and macrolide antimicrobials and trimethoprim in sewage sludge samples. A mixture of water/methanol (50:50, v/v) was found as the most efficient extraction solvent. A temperature of 100 degrees C and a pressure of 100 bar were chosen for extraction. Two cycles of 5 min each efficiently extracted at least 97% of the total extractable amount of all studied analytes from activated sludge. The limits of quantification (S/N= 10) varied between 3 and 41 microg/kg dry weight (dw) and the relative recoveries ranged between 78 and 142%. Additionally, the influence of pH and different LC/MS/MS systems on the absolute recoveries was assessed. Of the investigated antimicrobials sulfapyridin, sulfamethoxazole, trimethoprim, azithromycin, clarithromycin and roxithromycin were detected in municipal sewage sludge samples. Concentrations in activated sludge ranged up to 197 microg/kgdw. In comparison, results obtained by ultrasonic solvent extraction were significantly lower for sulfonamides and in tendency lower for macrolides.     

Sequential extraction of phosphorus in soil and sediment using a continuous-flow system

Distribution and mobility of phosphorus in soil and sediment are usually studied by sequential extraction. In the extraction procedure, a sample is treated with a series of reagents to distinguish the phases to which phosphorus is associated such as carbonate and iron or manganese oxides, etc. There have been a number of extraction schemes presented for phosphorus. At present, all of the existing schemes are carried out batchwise. Phosphorus contents derived from all sequences are operationally defined and depend on experimental conditions.An extraction procedure, which is a continuous-flow-based technique, was recently proposed by our group for metals in soils and sediments. The extraction is carried out in a closed chamber through which extractants are passed sequentially. In this paper, the system was investigated using the extraction scheme of Hieltjes and Lijklema to study distribution of phosphorus in three certified reference materials (CRMs). A number of fractions were collected for each reagent for subsequent colorimetric determination. The results are compared with those obtained from a batch extraction. The summation of phosphorus contents of all phases were compared with the certified values and with the values obtained from total digestion. These results have demonstrated that the continuous extraction system developed is also applicable for fractionation of phosphorus. Advantage and disadvantage are discussed.     

Kinetic models based in biomass components for the combustion and pyrolysis of sewage sludge and its compost

In the present work, pyrolysis and combustion of the sewage sludge (fresh and composted) have been simulated using five fractions: low stability organic compounds, hemicellulose, cellulose, lignin-plastic, and inorganic compounds. Thermal behavior and kinetic parameters (pre-exponential factor and apparent activation energy) of the main components of the sludge are similar to those reported for hemicellulose, cellulose, and lignin present in lignocellulosic biomass. Comparing non-isothermal thermogravimetric analysis data obtained from fresh and composted sewage sludge, it is possible to measure the efficiency of the composting process. Most of the biodegradable matter is volatized in a temperature range from 150 °C to 400 °C. Non-biodegradable organic matter volatilizes between 400 °C and 550 °C. In both, fresh and composted sludges, oxygen presence increases the mass loss rate at any temperature, but differences between pyrolysis and combustion are focused in two clearly defined ranges. At low temperature (200–350 °C), mass loss is related with a volatilization process. At higher temperature (350–550 °C), mass loss is due to slow char oxidation (oxidative pyrolysis).     

污泥与煤共热解过程中磷元素的挥发规律研究

污泥灰分中磷元素含量明显高于煤,其中主要的晶体态含磷化合物为磷酸铁钙和少量的磷酸铝。利用高频加热反应装置考察了污泥-神府煤混合物快速热解过程中磷元素挥发规律。结果表明,污泥-神府煤混合物热解后磷元素主要存在于热解焦中。磷元素挥发比例随污泥添加比例的增加先升高后降低,随热解温度的升高而增加。热解温度不高于1 100 ℃时,混合物中以有机磷的挥发为主,磷元素挥发比例不高于3.2%。热解温度高于1 200 ℃后无机磷中磷元素挥发明显,1 300 ℃下最高有33.0%的磷元素随热解气体挥发出。     

Sample preparation of sewage sludge and soil samples for the determination of polycyclic aromatic hydrocarbons based on one-pot microwave-assisted saponification and extraction

A microwave-assisted sample preparation (MASP) procedure was developed for the analysis of polycyclic aromatic hydrocarbons (PAHs) in sewage sludge and soil samples. The procedure involved the simultaneous microwave-assisted extraction of PAHs with n-hexane and the hydrolysis of samples with methanolic potassium hydroxide. Because of the complex nature of the samples, the extracts were submitted to further cleaning with silica and Florisil solid-phase extraction cartridges connected in series. Naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[e]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a,h]anthracene, benzo[g,h,i]perylene, and indeno[1,2,3-cd]pyrene, were considered in the study. Quantification limits obtained for all of these compounds (between 0.4 and 14.8 μg kg⁻¹ dry mass) were well below of the limits recommended in the USA and EU. Overall recovery values ranged from 60 to 100%, with most losses being due to evaporation in the solvent exchange stages of the procedure, although excellent extraction recoveries were obtained. Validation of the accuracy was carried out with BCR-088 (sewage sludge) and BCR-524 (contaminated industrial soil) reference materials.     

Dynamic fractionation of trace metals in soil and sediment samples using rotating coiled column extraction and sequential injection microcolumn extraction: A comparative study

Dynamic fractionation has been recognized as an appealing alternative to conventional equilibrium-based sequential extraction procedures (SEPs) for partitioning of trace elements (TE) in environmental solid samples. This paper reports the first attempt for harmonization of flow-through dynamic fractionation using two novel methods, the so-called sequential injection microcolumn (SIMC) extraction and rotating coiled column (RCC) extraction. In SIMC extraction, a column packed with the solid sample is clustered in a sequential injection system, while in RCC, the particulate matter is retained under the action of centrifugal forces. In both methods, the leachants are continuously pumped through the solid substrates by the use of either peristaltic or syringe pumps.A five-step SEP was selected for partitioning of Cu, Pb and Zn in water soluble/exchangeable, acid-soluble, easily reducible, easily oxidizable and moderately reducible fractions from 0.2 to 0.5 g samples at an extractant flow rate of 1.0 mL min⁻¹ prior to leachate analysis by inductively coupled plasma-atomic emission spectrometry.Similarities and discrepancies between both dynamic approaches were ascertained by fractionation of TE in certified reference materials, namely, SRM 2711 Montana Soil and GBW 07311 sediment, and two real soil samples as well. Notwithstanding the different extraction conditions set by both methods, similar trends of metal distribution were in generally found. The most critical parameters for reliable assessment of mobilisable pools of TE in worse-case scenarios are the size-distribution of sample particles, the density of particles, the content of organic matter and the concentration of major elements. For reference materials and a soil rich in organic matter, the extraction in RCC results in slightly higher recoveries of environmentally relevant fractions of TE, whereas SIMC leaching is more effective for calcareous soils.     

Pharmaceuticals and personal care products in biosolids/sewage sludge: the interface between analytical chemistry and regulation

Modern sanitary practices result in large volumes of human waste, as well as domestic and industrial sewage, being collected and treated at common collection points, wastewater treatment plants (WWTPs). In recognition of the growing use of sewage sludge as fertilizers and soil amendments, and the scarcity of current data regarding the chemical constituents in sewage sludge, the US National Research Council (NRC) in 2002 produced a report on sewage sludge. Among the NRC’s recommendations was the need for investigating the occurrence of pharmaceuticals and personal care products (PPCPs) in sewage sludge. PPCPs are a diverse array of non-regulated contaminants that had not been studied in previous sewage sludge surveys but which are likely to be present. The focus of this paper will be to review the current analytical methodologies available for investigating whether pharmaceuticals are present in WWTP-produced sewage sludge, to summarize current regulatory practices regarding sewage sludge, and to report on the presence of pharmaceuticals in sewage sludge.     

Concentration and characterization of dilute colloidal samples by potential-barrier field-flow fractionation

Summary Potential-barrier field-flow fractionation, which is a combination of potential-barrier chromatography and sedimentation field-flow fractionation, is shown to be a convenient and accurate method for the concentration and analysis (separation and characterization) ofdilute colloidal samples. Two sizes (0.158 and 0.271 μm) of haematite (α-Fe₂O₃) monodisperse colloidal samples diluted in volumes of up to 20 cm³ are used as model colloids. The particle diameters found by the present concentration procedure under various experimental conditions are in good agreement with those determined by conventional sedimentation field-flow fractionation, in which a small concentrated sample volume was injected directly into the column.