Mercury determination by CV-AAS in wastewater and sewage sludge from a stabilization pond system

The mercury concentrations in wastewater and sewage sludge of a stabilization pond system have been evaluated. The system is built by three parallel facultative ponds followed by two systems of three maturation ponds in series. The samples of wastewater and sludge were digested using nitric acid and placed into a Parr-type bomb for 4 h at 110 degrees C. Mercury was measured by Cold Vapour Atomic Absorption Spectrometry (CV-AAS) at 253.7 nm with sodium tetrahydroborate as reductant. The methodologies were checked with an USEPA quality control sample, a standard reference material from NIST and with another method of mineralization (cold mineralization) showing good results. Concentrations of mercury in wastewater between 1.47 +/- 0.75 microgl(-1) have been found at the entrance of the system and 0.74 +/- 0.0 microgl(-1) at the exit, while in sludge the results were between 0.29 +/- 0.12 microgkg(-1) in the facultative pond and 0.04 +/- 0.02 microgkg(-1) in the second maturation pond (exit).     

Mercury analysis in environmental samples by EDXRF and CV-AAS

The analysis of total Hg in various environmental matrices was investigated using energy dispersive X-ray fluorescence (EDXRF) for both powdered and digested samples and cold vapor atomic absorption (CV-AAS) for digested samples. Several microwave decomposition procedures were evaluated with respect to the determination of Hg by CV-AAS and EDXRF. The use of different acid mixtures, microwave power settings and decomposition times were compared as well as the analysis on wet and freeze-dried samples. A set of standard reference samples were used to evaluate the procedures: NBS Citrus leaves (1572), NRC Pine needles (1575), NRC Dogfish muscle tissue (DORM-2), NRC Dogfish liver tissue (DOLM-2), BCR Human hair (397), BCR Coking coal (181) and NRC Marine sediment (PACS-1). An H₂SO₄/HNO₃/H₂O₂ acid mixture was found to be optimal for the complete mineralization and digestion of biological samples for Hg by CV-AAS whereas for EDXRF both the HNO₃/H₂O₂ and H₂SO₄/HNO₃/H₂O₂ acid mixture gave good results. The detection limit of EDXRF could significantly be decreased (from 0.2 μg/g to 0.058 μg/g) by performing the analysis with digested samples. A good agreement was obtained between CV-AAS and EDXRF analysis. The obtained results were also in good agreement with certified values. The methods were applied to environmental samples (coal, trees, leaves, spinach, fish, sediments) and human hair in a coal mining area and in places where they use coal for cooking in Vietnam. Received: 24 February 1997 / Revised: 13 June 1997 / Accepted: 18 June 1997     

GC-MS analysis of organic compounds in wastewater and sewage sludge

A multimethod based on liquid-liquid extraction and solid-liquid extraction for the analysis of persistent organic pollutants in water and sludge from sewage treatment plants has been established. Traces of 22 organic compounds used in industry and personal care products (PCPs) were analyzed by GC/MS. The LODs for the analytes were less than 2.3 ng/L for wastewater and 31 microg/kg (dry weight matter) for sewage sludge. Satisfactory recoveries (70-130%) were achieved. The validated method permits the analysis of water and sludge samples at various stages of the treatment from different sewage treatment plants. Thus, the distribution between water and sludge as well as the dissipation of the compounds analyzed were balanced. By this means, the efficiency of different wastewater treatment plants (WWTPs) can be evaluated and measures can be taken to optimize the treatment process at different stages.     

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.     

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.     

Quantitative analysis of polycyclic aromatic hydrocarbons in sewage sludge from wastewater treatment plants.

Polycyclic aromatic hydrocarbons (PAHs) are an important group of organic contaminants present in sewage sludge. Due to their persistence and toxic potential, information about their presence in sewage sludge is needed in order to assess applicability on agricultural land. A method for the gas chromatographic-mass spectrometric (GC-MS) determination was developed and applied to the trace determination of PAHs present in sewage sludge samples from six wastewater treatment plants (WWTPs) differing in the type of treatment and the origin of wastewater. PAHs were extracted from freeze-dried samples by a dichloromethane-methanol (2:1) mixture in a sonication bath. The sludge extracts were cleaned-up by an alumina column. The method showed recovery values varying from 60 to 98%. Four surrogate standards ([2H8]naphthalene, [2H10]anthracene, [2H12]benzo[a]anthracene, and [2H12]benzo[ghi]perylene) were used for quantitation by GC-MS. A reference sludge sample was analysed in order to validate the method. The sum of the 16 US Environmental Protection Agency PAHs analysed in the sewage sludge samples varied from 1.13 to 5.52 mg/kg. No significant difference between the different WWTPs was found.     

On-line flash thermodesorption-GC-MS determination of PCB in sewage sludge

A flash thermodesorption-gas chromatography-mass spectrometry technique has been developed for the determination of polychlorobiphenyls (PCB), especially the highly toxic planar species, in sewage sludge. A modified Curie-point pyrolyzer was used; in this the flash-desorption temperature was controlled by selecting specific metal alloys for the pyrolysis wire. Samples (3 mg) were loaded into a quartz tube with the special heating wire wound around the outer wall. By this means rapid thermal desorption (TDS) was achieved whereas uncontrolled catalytic breakdown of the analytes was avoided. The thermodesorption unit was connected via a custom-built interface to the GC-MS detection system. The average limit of detection was 15 microgram kg(-1) sludge more than one order of magnitude better than the legal requirement.     

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.     

Accuracy of determination of trace metals in soil and sewage sludge

Errors in the analysis of liquid samples are often large enough to be important. For solid materials, additional potential complications arise in separating the determinand from the sample matrix and in controlling possible interferences from co-extracted species. These considerations have led to the development of a stepwise, co-ordinated approach by which a group of laboratories have achieved predefined standards of accuracy. Sample digestion has been examined. The analysis of digests has then been addressed; the control of analytical precision has been emphasised. Finally, a demonstration of overall comparability has been undertaken. The results are presented.     

Accuracy of determination of trace metals in soil and sewage sludge

Errors in the analysis of liquid samples are often large enough to be important. For solid materials, additional potential complications arise in separating the determinand from the sample matrix and in controlling possible interferences from co-extracted species. These considerations have led to the development of a stepwise, co-ordinated approach by which a group of laboratories have achieved predefined standards of accuracy. Sample digestion has been examined. The analysis of digests has then been addressed; the control of analytical precision has been emphasised. Finally, a demonstration of overall comparability has been undertaken. The results are presented.     

Determination of Hg in water and wastewater samples by CV-AAS following on-line preconcentration with silver trap

An online mercury preconcentration and determination system consisting of cold vapor atomic absorption spectrometry (CV-AAS) coupled to a flow injection (FI) method was studied. The method was developed involving the determination of ng/L levels of mercury retained on the silver wool solid sorbent. Experimental conditions such as sample volume, flow rate, stability of the column and effect of foreign ions on the determination of trace amounts of mercury were optimized. The detection limit is 3 ng/L and dynamic range 10–250 ng/L require only 50 mL of sample. The relative standard deviations (RSD) of the determinations are below 4%. The presence of common metal ions, such as K+, Na⁺, Cu²⁺, Pb²⁺, Fe³⁺, Ni²⁺, and Mn²⁺, does not interfere with the measurement of mercury by this method. The method was successfully applied to the determination of mercury in water and wastewater samples.     

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.     

Two-step upflow anaerobic sludge bed system for sewage treatment under subtropical conditions with posttreatment in waste stabilization ponds

A pilot-scale sewage treatment system consisting of two upflow anaerobic sludge bed (UASB) reactors followed by five waste stabilization ponds (WSPs) in series was studied under subtropical conditions. The first UASB reactor started up in only 1 mo (stable operation, high chemical oxygen demand [COD] removal efficiency, low volatile fatty acids concentration in the effluent, alkalinity ratio above 0.7, biogas production above 0.1 Nm3/kg of CODremoved). Removal efficiencies up to 90% were obtained in the anaerobic steps at a hydraulic retention time of 6 + 4 h (80% removal in the first step). Fecal coliform removal in the whole system was 99.9999% (99.94% in anaerobic steps and 99.98% in WSPs). COD balances over UASB reactors are provided. A minimum set of data necessary to build COD balances is proposed. Intermittent sludge washout was detected in the reactors with the COD balances. Sludge washout from single-step UASB reactors should be monitored and minimized in order to ensure constant compliance with discharge standards, especially when no posttreatment is provided. The system combined high COD and fecal coliform removal efficiency with an extremely low effluent concentration, complying with discharge standards, and making it an attractive option for sewage treatment in subtropical regions.     

Simultaneous determination of the endocrine disrupting compounds nonylphenol, nonylphenol ethoxylates, triclosan and bisphenol A in wastewater and sewage sludge by gas chromatography-mass spectrometry

An integrated analytical method for the simultaneous determination of 4-n-nonylphenol (4-n-NP), nonylphenol monoethoxylate (NP1EO), nonylphenol diethoxylate (NP2EO), bisphenol A (BPA) and triclosan (TCS) in wastewater (dissolved and particulate phase) and sewage sludge was developed based on gas chromatography-mass spectrometry. Chromatographic analysis was achieved after derivatization with bis(trimethylsilyl)trifluoroacetamide (BSTFA). Extraction from water samples was performed by solid-phase extraction (SPE). The optimization of SPE procedure included the type of sorbent and the type of the organic solvent used for the elution. Referred to solid samples, the target compounds were extracted by sonication. In this case the optimization of the extraction procedure included the variation of the amount of the extracted biomass, the duration and the temperature of sonication and the type of the extraction organic solvent. The developed extraction procedures resulted in good repeatability and reproducibility with relative standard deviations (RSDs) less than 13% for all the tested compounds for both types of samples. Satisfactory recoveries were obtained (>60%) for all the compounds in both liquid and solid samples, except for 4-n-NP, which gave recoveries up to 35% in wastewater samples and up to 63% in sludge samples. The limits of detection (LODs) of the target compounds varied from 0.03 (4-n-NP) to 0.41 microg l(-1) (NP2EO) and from 0.04 (4-n-NP) to 0.96 microg kg(-1) (NP2EO) for liquid and solid samples, respectively. The developed methods were successfully applied to the analysis of the target compounds in real samples.     

An analytical method for the simultaneous trace determination of acidic pharmaceuticals and phenolic endocrine disrupting chemicals in wastewater and sewage sludge by gas chromatography-mass spectrometry

This article presents an analytical method based on solid-phase extraction (SPE) and gas chromatography coupled with mass spectrometry for the simultaneous determination of the most frequently used acidic pharmaceutical residues, ibuprofen, diclofenac, naproxen and ketoprofen (KFN), and phenolic endocrine disruptors, bisphenol (BPA), triclosan (TCS), nonylphenol, nonylphenol monoethoxylate and nonylphenol diethoxylate, in wastewater and sewage sludge samples. In the first phase of the study, each compound has been characterized individually and afterwards in mixture as a trimethylsilyl derivative in order to identify the characteristic ions (m/z ratio) constituting the mass spectrum and to choose the ions for quantification and confirmation. Subsequently, derivatization was evaluated by testing different variables such as the volume of the derivatization solvent bis(trimethylsilyl)trifluoroacetamide and the effect of each catalyst, pyridine and 1% trimethyl chlorosilane, in the derivatized solution. For the analysis of wastewater samples, two commercial SPE cartridges, C18 and Oasis HLB, were compared for their extraction efficiency of the target compounds. The key parameter of extraction procedure included the effect of pH (2.5, 5.3 and 7) of the loading solution. For solid samples, parameters such as the extracted biomass, the volume of the extraction organic solvent and the effect of matrix interferences in chromatographic analysis were evaluated. By using C18 cartridges as purification procedure and ultrasound sonication, satisfactory mean relative recoveries with BPA-d16 and meclofenamic acid as surrogates were obtained ranging from 91% to 117% for wastewater and 84% to 107% for sewage sludge samples. Nine-point calibration of the standard mixture was performed by linear regression analysis with a correlation coefficient >0.99 for all the tested compounds. Limits of detection for the developed methods were established between 0.3 (KFN) and 14.8 (BPA) ng L⁻¹, and 15.0 (TCS) and 32.9 (BPA) ng g⁻¹ for wastewater and sewage sludge, respectively. Application to real samples of the wastewater treatment plant in Athens, the capital of Greece, demonstrated the presence of all tested compounds in most of the samples.     

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.     

Preparation of a sewage sludge laboratory quality control material for butyltin compounds and their determination by isotope-dilution mass spectrometry

The characterisation of a laboratory quality control material (QCM) for dibutyltin (DBT) and tributyltin (TBT) in sewage sludge is described. The reference values were determined by the use of two different types of isotope-dilution mass spectrometry: gas chromatography–mass spectrometry and gas chromatography–inductively coupled plasma mass spectrometry. To avoid possible analytical errors such as non-quantitative extraction and species degradation during sample preparation, different extraction methods were tested (microwave- and ultrasound-assisted extraction and mechanical stirring). The reference values were based on the unweighted means of results from the homogenisation and characterisation studies. The reference values obtained were 1,553 ± 87 and 534 ± 38 ng Sn g^-1 for DBT and TBT, respectively. In the uncertainty budget estimation, the sample inhomogeneity and between-method imprecision were taken into account. The concentrations of DBT and TBT in QCM are similar to those in the harbour sediment certified reference material PACS-2. Likewise, the levels of DBT and TBT are in the range of these compounds normally present in sewage sludge worldwide. In the future, the QCM will be used for an intercomparison study on DBT and TBT in sewage sludge, and as a day-to-day QCM during studies concerning the application of sewage sludge as an additive to artificial soil or as a raw material in civil engineering construction.     

New quality-control materials for the determination of alkylphenols and alkylphenol ethoxylates in sewage sludge

The determination of alkylphenols in sewage sludge is still hindered by the complexity of the matrix and of the analytes, some of which are a mixture of isomers. Most of the methods published in the literature have not been validated, due to the lack of reference materials for the determination of alkylphenols in sludge. Given this situation, the objectives of the present study were to develop a new quality-control material for determining octylphenol, nonylphenol and nonylphenol monoethoxylate in sludge. The material was prepared from an anaerobically digested sewage sludge, which was thermally dried, sieved, homogenized and bottled after checking for the bulk homogeneity of the processed material. Together with the sewage sludge, an extract was also prepared, in order to provide a quality-control material for allowing laboratories to test the measuring step. The homogeneity and 1-year stability of the two materials were evaluated. Statistical analysis proved that the materials were homogeneous and stable for at least 1?year stored at different temperatures. These materials are intended to assist in the quality control of the determination of alkylphenols and alkylphenol ethoxylates in sewage sludge.

Validation of a method for extraction of polycyclic aromatic hydrocarbons from sewage sludge and analysis by GC-MS

In the present study, the solid–liquid extraction with low temperature purification was validated for the determination of 16 polycyclic aromatic hydrocarbons from sewage sludge by gas chromatography-mass spectrometry. Recoveries ranged 70–114% for naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene and chrysene, while the compounds benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene, dibenzo[a,h]anthracene and benzo[g,h,i]perylene showed recoveries of between 40 and 70%. The relative standard deviation was less than 13% for all of the compounds. Negative matrix effect was observed on the 10 compounds with less retention time in the chromatographic analysis and positive matrix effect noticed on the others. The limits of quantification were from 2 to 20 μg kg^?1, about 30 times less than the maximum residue limit allowed in sludge by the European Union. The validated method produced quantification of 11 PAHs in one sludge sample at concentrations ranging 20–2000 μg kg^?1.