A comparison of three analytical techniques for the measurement of steroidal estrogens in environmental water samples

Research into the analysis and monitoring of steroidal estrogens has grown significantly over the last decade, resulting in the emergence of a range of applicable techniques. In this study, three popular techniques, gas chromatography-mass spectrometry (GC-MS), gas chromatography-tandem mass spectrometry (GC-MS-MS) and liquid chromatography-tandem mass spectrometry (LC-MS-MS) for the analysis of three highly potent steroidal estrogens in the aquatic environment have been compared. It has been observed that overall, the three techniques appear comparable in generating similar estrogen concentrations for river and effluent samples. Of the three techniques, the GC-MS technique is the simplest to operate, but fails to detect the estrogens at the lower-end of environmentally relevant concentrations. The tandem MS techniques are more selective than MS, and therefore able to detect lower concentration levels of the three steroidal estrogens of interest. However, the LC-MS-MS technique is more susceptible to matrix interferences for the analysis of samples, resulting in a reduction of the signal-to-noise ratio and a subsequent reduction in reliability and stability compared to GC-MS-MS. With the GC-MS-MS technique offering increased selectivity, the lowest limits of detection, and no false positive identification, it is recommended to be the preferred analytical technique for routine analysis of estrogens in environmental water samples.     

Determination of 210Pb in environmental samples

Summary Measurement of ²¹⁰Pb has gained a highly scientific attention due to its wide range of environmental applications. The most commonly used analytical techniques: gamma-spectrometry, beta-counting and alpha-spectrometry were used to measure environmental samples (geological, soil, sediment). Our paper is aiming at comparing the capabilities and limits of application of these three different analytical techniques for ²¹⁰Pb measurement in various environmental samples. In addition, analytical data of ²¹⁰Pb measurements with the three different techniques (gamma-spectrometry, beta-counting and alpha-spectrometry) are discussed to highlight the degree of comparability and the most probable sources of discrepancies and errors. Based on the demanded investigation, one analytical technique will be chosen for routine analysis, while the other techniques, if they are available, could be used for analytical quality assurance measures. It was essential to compare the analytical efficacy of each technique, which differ concerning the detection limit (MDA), sensitivity, analytical effort, the duration of analysis and waiting time before analysis.     

Comparison of Three Techniques for Lipid Removal from Seal Blubber: Gel Permeation,Acid Treatment,and Dialysis with Semipermeable Membrane

Abstract

Harbor seal blubber samples were analyzed for PCDD/Fs and PCBs by splitting the initial extract into three aliquots and applying three different techniques for lipid removal (the first step of sample cleanup methodology for GC-HRMS analysis): gel permeation chromatography (GPC), sulfuric acid treatment, and dialysis through semipermeable membrane. Correlation coefficients of analyte concentrations obtained from three sets of replicate samples ranged from 0.965 to 0.994. In addition, a number of seal blubber samples were processed without pre-extraction using only the dialysis technique. The analyte concentrations in these samples correlated well with the analyte concentrations obtained from dialyzed blubber extracts (correlation higher than 0.998). For all analyses (PCDD/Fs, NO- and MO-PCBs) the average surrogate standard recoveries for the GPC and dialysis techniques varied from 68 to 111%. The recoveries for PCDD/Fs and MO-PCBs standards ranged from 61 to 89% and 36 to 43% for the NO-PCBs when the acid treatment technique was used. Dialysis was proven to be an efficient technique for lipid removal of biological samples in comparison with the GPC and acid treatment techniques.     

Application of different activation analysis techniques for determination of trace elements in human blood

One of the requirements of stable isotope tracer technique is detection of two isotopes of same element. It is preferable to use instrumental techniques in order not to contaminate the samples. Different instrumental nuclear techniques namely neutron activation analysis (NAA), photon activation analysis (IPAA), and prompt gamma ray activation analysis (PGAA) were tried on human blood samples. The techniques were found to be complementary to each other, NAA being the most sensitive of the three. Zinc is choosen for validation work among the three feasible elements (Zn, Cr, Se) for stable isotope tracer technique. As NAA was not sufficient to detect two isotopes of Zn, a radiochemical separation scheme was developed later.     

Comparison of APPI, APCI and ESI for the LC-MS/MS analysis of bezafibrate, cyclophosphamide, enalapril, methotrexate and orlistat in municipal wastewater

The applicability of three different ionization techniques: atmospheric pressure photoionization (APPI), atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI) was tested for the liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis of five target pharmaceuticals (cyclophosphamide, methotrexate, bezafibrate, enalapril and orlistat) in wastewater samples. Performance was compared both by flow injection analysis (FIA) and on-column analysis in deionized water and wastewater samples. A column switching technique for the on-line extraction and analysis of water samples was used. For both FIA and on-column analysis, signal intensity and signal-to-noise (S/N) ratio of the target analytes in the three sources were studied. Limits of detection and matrix effects during the analysis of wastewater samples were also investigated. ESI generated significantly larger peak areas and higher S/N ratios than APCI and APPI in FIA and in on-column analysis. ESI was proved to be the most suitable ionization method as it enabled the detection of the five target compounds, whereas APCI and APPI ionized only four compounds.     

Comparison of 14 MeV-NAA, k0-NAA and ED-XRF for air pollution bio-monitoring

In this paper the performances and the limitations of three multi-elementary analysis techniques are compared applied to a study of air pollution biomonitoring in Morocco. These techniques are: (1) 14 MeV neutron activation analysis (14 MeV-NAA), (2) thermal neutron activation analysis using the k ₀ quasi-absolute method (k ₀-NAA) and (3) energy dispersive X-ray fluorescence analysis (ED-XRF). The experimental procedures and the control of the analytical results using certified reference materials are described and discussed. The three methods were confronted for the analysis of lichens, mosses and tree-barks. The complementarity of these methods enabled us to determine 43 elements in different samples. The most suitable method for each element was selected according to the sensitivity and selectivity necessitating the minimum corrections of the matrix effects and/or the interfering reactions.     

Simultaneous determination of traces of iron, cobalt, nickel, copper, mercury and lead in water by energy-dispersive x-ray fluorescence spectrometry after preconcentration as their piperazino-1,4-bis(dithiocarbamate) complexes

A bidentate chelating agent has been proposed to preconcentrate seven metal ions dissolved in an aqueous sample for their simultaneous determination using energy-dispersive x-ray fluorescence spectrometry. The metal ions are precipitated as their polymeric piperazino-1,4-bis(dithiocarbamate) chelates, which are then collected by vacuum filtration on a Millipore membrane filter for direct examination by x-ray fluorescence analysis. Iron, cobalt, nickel, copper and zinc are determined by means of their K x-rays and mercury and lead by means of their L x-rays. A detection limit in the μg1⁻¹ range can be achieved for all metals tested in 250-ml water samples with a counting time of 600 s. Effective precipitation of all metals occurs at pH 6–7. The recoveries of eight analyses of the metals in a multielement standard using the proposed method ranged from 97 to 105% and the precision ranged from 2.3 to 3.1%. High concentrations of calcium and magnesium do not interfere with the method. The method is simple, sensitive and accurate, and has been used for the simultaneous determination of the seven metals under study in environmental samples and synthetic mixtures.     

The determination of antimony in nodular cast iron by wavelength-dispersive x-ray fluorescence spectrometry

Antimony is determined in cast irons by wavelength-dispersive x-ray fluorescence spectrometry. Excitation and detection conditions are evaluated for the three most intense x-rays of antimony, i.e., the K_α, L_α and L_β lines. Standard samples were obtained by precise determination of the antimony content of some specimen cast irons by neutron activation analysis. Calibration graphs are linear from 0 to 200 mg kg^?1. The precision of the determination by means of the most sensitive Sb L_α line, using a chromium tube and a 5-min measuring time, ranges from 6% for samples containing 20 mg kg^?1 antimony, to 1% for samples containing 200 mg kg^?1.     

Measurement of lead isotope ratios in wine by ICP-MS and its applications to the determination of lead concentration by isotope dilution

 Methods are described for the accurate and precise determination of lead concentrations and the isotopic composition of lead in wine samples using Inductively Coupled Plasma Mass Spectrometry (ICP-MS). This method needs little sample preparation. A comparison with lead isotope ratios measured by Thermal Ionization Mass Spectrometry (TIMS) in three wine samples reveals a good agreement between the two techniques. The lead concentration in three certified wine samples were measured by isotope dilution (ID) and the results are compared with those obtained by external calibration ICP-MS. Received: 10 June 1996/Revised: 23 September 1996/Accepted: 30 September 1996     

The use of ion-induced x-rays for spectrochemical analysis

The application of ion-induced x-rays to spectrochemical analysis was examined by means of a dispersive method with a flat crystal and a 200-kV ion accelerator. For x-rays of longer wavelength than 10 Å, x-ray count rates of the order of 10⁴–10⁵ c.p.s. were obtained; the use of heavy ions such as Kr⁺, Ne⁺ and O⁺ was shown to be effective for x-rays shorter than about 30 Å, while protons were more efficient for longer wavelengths. X-Ray excitation efficiencies are almost independent of the atomic shell with which the x-rays are associated and are dependent on wavelength only, indicating that almost all elements can yield K, L or M x-rays of considerable intensity. The x-ray excitation method by proton and heavy ion bombardment was applied to the determination of some light elements, F, O, N and Be. Detection limits of 10 p.p.m. could be readily achieved for these elements.     

环境与生物体系中铝形态分析技术的新进展

铝的形态分析是研究环境和生物体系中铝的毒性、生物有效性和传输机理的关键。从IUPAC2000，72，1453和Analyst2001，126(2)对元素形态概念的最新定义，在过去20年来，形态分析都是依据操作手段来进行“组形态”(group species)分析。然而，随着近5年来分析技术的发展，对铝的形态分析逐步达到了“单形态”(individual species)分析的水平。从以下两个方面对该领域的最新进展进行了评述，即：(1)组形态分析(fractionation)：离子交换、电化学分析和流动注射；(2)单形态分析(speciation)：联用技术、核磁共振和计算机拟合。     

Thermo-programmed reduction study of Pt/WO<Subscript>x</Subscript>–ZrO<Subscript>2</Subscript> materials by thermogravimetry

The thermo-programmed reduction study of Pt/WO_x–ZrO₂ materials prepared with different tungsten loading were performed by thermogravimetry. The samples were synthesized by impregnation method and calcined at 600, 700 and 800°C. The characterizations of both un-calcined and calcined materials were carried out using different techniques: thermal analysis (TG and DTA), X-ray diffraction (XRD) and thermo-programmed reduction (TPR). TG and DTA analysis of un-calcined were used to determination of calcination temperatures of the samples. XRD diffractograms were useful to help us in the determination of phase presents. TPR profiles showed between three and four events at different temperatures attributed to platinum reduction and the different stages of tungsten specie reduction.     

Characterization of paper finishes by use of infrared spectroscopy in combination with canonical variate analysis

The finishing process used by the paper industry involves subjecting the paper surface to the action of chemicals and physical treatments in a series of operations intended to provide an end-product suitable for its intended use. In this work, we studied various paper finishes by using infrared spectra processed with appropriate chemometric techniques. To this end, we used a wide range of paper samples supplied in various finishes (coated, offset and cast-coated) by several paper manufacturers. Fourier transform middle-infrared (FTIR) spectra for the paper samples were recorded by using an ATR module, and reflectance near-infrared (NIR) spectra with the aid of a fibre-optic probe. Both techniques are fast and require no sample pretreatment.The primary aim of this work was to develop a new methodology affording the accurate classification and identification of paper finishes in samples other than those used to construct the calibration model. To this end, we used the discriminant chemometric techniques principal component analysis (PCA) and canonical variate analysis (CVA), application of which was followed by that of the k-nearest neighbour algorithm to the samples in the prediction set. This procedure was also used to classify the coated samples into three subgroups. Both FTIR and NIR spectroscopy allowed most of the samples in the prediction sets to be accurately classified and identified.     

Fingerprinting and source identification of an oil spill in China Bohai Sea by gas chromatography-flame ionization detection and gas chromatography–mass spectrometry coupled with multi-statistical analyses

This paper describes a case study in which advanced chemical fingerprinting and data interpretation techniques were used to characterize the chemical composition and determine the source of an unknown spilled oil reported on the beach of China Bohai Sea in 2005. The spilled oil was suspected to be released from nearby platforms. In response to this specific site investigation need, a tiered analytical approach using gas chromatography–mass spectrometry (GC–MS) and gas chromatography-flame ionization detection (GC-FID) was applied. A variety of diagnostic ratios of “source-specific marker” compounds, in particular isomers of biomarkers, were determined and compared. Several statistical data correlation analysis methods were applied, including clustering analysis and Student's t-test method. The comparison of the two methods was conducted. The comprehensive analysis results reveal the following: (1) The oil fingerprinting of three spilled oil samples (S1, S2 and S3) positively match each other; (2) The three spilled oil samples have suffered different weathering, dominated by evaporation with decrease of the low-molecular—mass n-alkanes at different degrees; (3) The oil fingerprinting profiles of the three spilled oil samples are positive match with that of the suspected source oil samples C41, C42, C43, C44 and C45; (4) There are significant differences in the oil fingerprinting profiles between the three spilled oil samples and the suspected source oil samples A1, B1, B2, B3, B4, C1, C2, C3, C5 and C6.     

Determination of Trace Elements in Aerosol Samples Collected on Polycarbonate Filters by Atomic Absorption Spectrometry

Abstract

The multi-element analysis of aerosol samples collected on polycarbonate filters and the wet digestion procedure in open vessel were investigated. The concentrations of Na, K, Ca, Mg and Zn were determined by flame atomic absorption spectrometry with a micro injection system while Cd, Pb, Cu, Ni and V were determined by graphite furnace atomic absorption spectrometry (AAS).

NIES N[ddot] 8 “Vehicle Exhaust Particulate” Certified Reference Material from the Japan Environment Agency was used to study the decomposition of the samples. Different treatments were applied in order to completely dissolve the aerosol samples. It was found that, from all the methods tested, attack with micro-quantities of HNO₃ and HCIO₄ in an air pressure digestion system was the best procedure for the determination of the elements by AAS.

The recommended method was appropriate for all elements and it was applied to real samples. Two nondestructive analytical techniques for the determination of Na, K, Ca, Mg, Zn and Pb have been compared with the proposed method: proton induced X-ray emission (PIXE) and neutron activation analysis (NAA). Results obtained by the application of these three techniques were similar.     

Update on solid-phase extraction for the analysis of lipid classes and related compounds

This article provides information on the different procedures and methodologies developed when solid-phase extraction (SPE) is used for lipid component separation. The analytical systematics, established by different authors and designed to separate groups of compounds and also specific components by using a combination of chromatographic supports and solvents are presented. The review has been divided into three parts, which we consider well defined: edible fats and oils, fatty foods and biological samples. Separations of non-polar and polar lipids is the most extensive systematic, although many other published methods have been established to isolate specific components or a reduced number of components from edible fats and oils, fatty foods or biological samples susceptible to further analysis by other quantitative techniques.     

Comparative analysis of bias in the collection of airborne pollutants: Tests on major aromatic VOC using three types of sorbent-based methods

This study was undertaken to establish one of the most reliable sampling methods and to precisely evaluate the bias involved in the collection of airborne pollutant samples. For the purpose of our study, we investigated the performance of three different types of sampling techniques by measuring major aromatic volatile organic compounds (VOC) in outdoor air; the target analytes specifically include benzene, toluene, ethylbenzene, and xylene (commonly called BTEX). As the first step of our approach, we designed and developed a multi-channel sampling system consisting of a six-port mass flow controller (SJU-MFC) system. Because this system allowed the collection of up to six replicate samples, our measurement results were analyzed and screened statistically for the derivation of high-quality BTEX data. The feasibility of this sampling system was further tested through a comparison with concurrent measurement data sets obtained by two additional, but independent, sampling techniques: (1) automatic continuous sampler (ACS) and (2) on-line GC (O-GC) system. Based on the data sets collected concurrently by three different sampling methods, we attempted to evaluate the compatibility of sampling techniques. Although the results obtained by SJU-MFC system were not statistically different from those of the O-GC system, they were moderately distinguishable from those of ACS. Such patterns were seen consistently, when examined by correlation analysis. The overall results of our study thus generally point out that the compatibility of data sets, when the proper caution is taken, improve significantly among different sampling methodologies.     

Elemental concentrations in sediments of the Patras Harbour, Greece, using INAA, ICP-MS and AAS

Twenty marine sediment samples, selected downcore from six sediment cores, which were retrieved from the Patras Harbour, were studied for their elemental composition using three analytical techniques: INAA, ICP-MS and AAS. Standard reference materials were used to verify the accuracy of the analysis techniques. In total, the concentrations of 30 major, minor and trace elements were measured. The vertical distribution of most elements in the examined cores could be characterized as relatively uniform. The eastern part of the harbour seems to be more polluted in respect to some elements (Ag, Br, Cd, Cr, Cu, Pb and Zn) compared to the western one. The concentrations of a number of elements (As, Cd, Cr, Cu, Ni, Pb and Zn) determined in the sediment samples of the present work are discussed regarding to those obtained from other harbours in the world and compared against sediment quality guidelines (SQGs) to assess the ecotoxicological significance of the sediment contaminants to benthic biota.     

Analytical determination of microelements in well waters

Well water analysis was carried out starting with liquid samples which have been evaporated to dryness. The salt deposit crust has ensured an enrichment in microelements which were approximately determined by emission spectroscopy. Once the order of magnitude was established, the exact measurements were carried out based on the following techniques: mass spectrometry, atomic absorption spectrophotometry, activation with slow neutrons, and γ-spectrometry. The results obtained are the average values of at least three methods employed. *** DIRECT SUPPORT *** A1353055 00005     

Study by thermal analysis of mortars belonging to wall paintings corresponding to some historical buildings of Sevillian art

Mortars taken from the walls of three historical buildings in Seville: Pond of Patio de las Doncellas in Real Alcazar of Seville, the Monastery of Santa Maria de las Cuevas and the Church of El Salvador were investigated. The techniques employed were thermogravimetry (TG), differential thermal analysis (DTA), XRD, FTIR, SEM with EDAX, Bernard calcimeter, granulometry, mercury intrusion porosimetry and mechanical strength tests. The majority of the studied mortars consist of calcite and silica. Gypsum was detected in samples of four mortars from the Santa Maria de las Cuevas Monastery and two from the El Salvador Church, whose samples were taken from the upper layers of the walls, but gypsum was not detected in the internal mortars layers. Only in two of the samples of the Monastery, the presence of cellulosic material as an organic additive was detected. All the studied mortars could be regarded hydraulic, so much by results from ratios between mass loss due to CO₂ and H₂O, hydraulic module and assays of compressive strength. The values obtained by these three techniques are related, providing good agreements between them. These results give useful information that aids in understanding the technology of historic mortars, and how to plan the restoration of these wall paintings.