Monitoring Airborne Particulate Mass by Beta Absorption

Abstract

A prototype airborne particulate mass monitor, using the principle of beta radiation absorption, has been fabricated and evaluated on airborne particulate matter. A detection sensitivity of 80 μg/cm² was attained. A series of samples were collected, and a comparison made between the gravimetric and beta absorption results obtained on each sample. This study demonstrated the feasibility of fabricating a fully automated system for the collection and analysis of airborne particulate mass, using the principle of beta absorption attenuation.     

Semi-Preparative Reverse Phase HPLC Fractionation of Pesticides from Edible Fats and Oils

Abstract

A semi-preparative (25 cm × 9.4 mm i.d.) HPLC ODS-bonded silica column was evaluated for the fractionation of pesticides from edible fats and oils of both animal and vegetable origin. Using acetonitrile as a mobile phase, organochlorine and organophosphorous pesticides with a wide range of polarity were eluted in the first 40 ml of eluate. Co-eluted lipid material ranged from 0 to 35 mg for 500 mg injections, depending on sample type. Excessively “dirty” samples (e.g., tallow) were further cleaned up on small Florisil columns. Recoveries of selected pesticides from fortified samples, which were determined by gas chromatography with electron capture and flame photometric detectors, ranged from 80 to 108%.     

Layer-like fatigue is induced during mechanical pulping

The question whether fatigue is induced during mechanical pulping was addressed experimentally. The grinding process was interrupted to image partly ground spruce samples. The grinding was performed at five different feed velocities using two different grindstones. This approach allowed creating an in situ snapshot of the developing grinding zone in the wood samples. The depth profiles of the stiffness modulus and nm-scale pores, close to and within, the grinding zone were quantified by ultrasonic pitch-catch measurements and thermoporosimetry. To perform these profiling measurements, wood material was iteratively removed layer-by-layer with a microtome from the sample surface after taking the snapshot. The grinding-induced changes in cell morphology inside the sample were imaged using microcomputed tomography, whereas the changes on the surface of the samples were imaged with optical microscopy and SEM. A layer that penetrated 0.5–1.5 mm into the sample exhibiting up to 80% decreased stiffness modulus—compared to the unaltered sample parts—was detected when the Wave-type grindstone was employed. The corresponding layer thickness was 0.3 mm with the conventional grindstone. The results match previously measured temperature profiles, and confirm the Atack-May hypothesis that grinding induces a fatigue layer. Confirming this old, widely used hypothesis is significant for the field of energy efficiency research related to mechanical pulping and may provide new opportunities for grinding research.     

Determination of Zearalenol and Zearalenone Using Electrochemical Detection

Abstract

A method is described for the determination of zearalenol and zearalenone in corn using electrochemical detection. the sample is extracted with chloroform, and the extract is cleaned up by liquid-liquid partition. Zearalenol and zearalenone are resolved by liquid chromatography (LC), using a C₁₈ column and a mobile phase consisting of 35 + 25 + 40 CH₃ CN + MeOH + H₂O and 0.02 mole/L sodium acetate buffered at pH 6.5. Zearalenol and zearalenone were detected with an electrochemical detector at an applied potential of +0.95V vs Ag/AgCl. Average recoveries of zearalenol and zearalenone in corn samples spiked at levels of 25–1000 ng/g were 104,2 and 97.5%, respectively. the coefficients of variation for the proposed method were 10.8% for zearalenol and 8.8% for zearalenone.     

Determination of alkylphenols and their short-chained ethoxylates in Polish river waters

A simple and robust analytical method for analysis of octyl- and nonylphenol as well as their short-chained ethoxylates in river water was proposed. Quantification of these analytes was performed by high-performance liquid chromatography with fluorescence detection after isolation using solid phase extraction with polytetrafluoroethylene sorbent. The method allowed one to obtain about 80–100% recovery for octylphenol and its ethoxylates and 70–80% for nonylphenol and its ethoxylates. Also, there was no need for additional sample cleaning before chromatographic analysis. The limit of detection was 0.01?µg?L^?1 for octylphenol and its ethoxylates and 0.03?µg?L^?1 for nonylphenol and its ethoxylates. The proposed method was used for quantitation of octyl- and nonylphenol together with their short-chained ethoxylates. Nonylphenol, nonylphenol mono- and diethoxylates were detected at concentrations ranging from 0.12 to 0.53?µg?L^?1. Octylphenol, octylphenol mono- and diethoxylates were detected in four out of eleven samples at concentrations ranging from 0.03 to 0.17?µg?L^?1. High concentrations of nonylphenol and its ethoxylates were found in the samples, despite the fact that their use in European countries was forbidden several years ago.     

Determination of Fumonisin B1 in Corn by High Performance Liquid Chromatography With Fluorescence Detection

Abstract

A method is described for the determination of fumonisin B1 in corn. The method involves sample extraction with methanol:water (75:25) and partial purification using a solid phase extraction. Fumonisin B1 is reacted with naphthalene-2,3-dicarboxaldehyde (NDA) to produce a highly fluorescent derivative, 1-cyano-2-alkyl-benz[f]isoindole (CBI) and then separated from the sample matrix on a reverse phase C-18 column with a mobile phase of acetonitrile:water:acetic acid (55:45:1). The NDA-derivative is quantitated by fluorescence detection at 410 nm excitation and a 440 nm, long past emission filter. Recoveries of fumonisin B1 added to corn at levels of 0.25–20.0 μg/g averaged 88.1% with a coefficient of variation of 10.3%. Confirmation of fumonisin B1 in corn samples was accomplished by fast atom bombardment (FAB) spectroscopy.     

A HPLC Screening Procedure for Sulfamethazine Residues in Pork Tissues

Abstract

A sensitive and specific screening procedure is described for the quantitative detection of sulfamethazine residues in pork kidney, liver and muscle. Initial screening is by both the Bratton-Marshall reaction, and by high pressure liquid chromatography (HPLC); quantitation is by HPLC; identification is then confirmed by means of thin-layer chromatography (TLC) of the derivatized standards and the unknown from the Bratton-Marshall reaction. Only one extraction of a 50g sample is needed, one portion (10g tissue equivalent) is used for the colorimetric reaction and TLC confirmation, and another portion (25g tissue equivalent) is used for quantitative HPLC determination. Standard curves for sulfamethazine are constructed for each tissue at 50, 100, 200 and 500 ppb levels. The average mean recovery for all tissues at all levels is 78.2%. The method is verified by a 150 sample survey using 50 samples of each tissue from local supermarkets. Approximately 4% of the samples show contamination ranging from a level of 100 ppb to 3 ppm.     

Determination of hydrogen in stainless steels by spark-source mass spectrometry

A spark-source mass spectrometric (SSMS) method capable of determining traces of hydrogen in micro-volumes of metals was developed by using a pointed metal probe technique. The hydrogen background was decreased to μg g^?1 levels by the combination of a method in which the sample in the ion source is baked under vacuum at 323–343 K for more than 25 ks and a liquid nitrogen or liquid helium cryogenic pump method. This method was applied to the analysis of austenitic stainless steels at μg g^?1 hydrogen levels, and the relative standard deviation was within 20% for samples with hydrogen concentrations ranging from 2 to 4 μg g^?1. The relative sensitivity coefficent was 2.3 (Fe=1).     

HPLC Determination of Valproic Acid in Human Serum Using Ultraviolet Detection

Abstract

A sensitive HPLC method with minimal sample preparation and good reproducibility for the determination of valproic acid in serum is described. Serum samples were precipitated using acetonitrile containing diazepam as the internal standard. Chromatography was performed on a Hewlett Packard model 1090 equipped with an octadecylsilane column and a Beckman model 163 variable wavelength detector. The drug and internal standard were eluted isocratically using a mobile phase consisting of 0.01M sodium phosphate monobasic solution, pH 2.3 and acetonitrile (63:37 v/v) followed by a gradient to flush the column before the next sample injection. The flow rate was 2.5 mL/min, the injection volume was 25 μL and the effluent was monitored at 210 nm. The serum standard curve was linear from 2.5-200.0 μg/mL with a correlation coefficient of 0.9994. Day-to-day precision for quality control samples (10.0, 25.0, 75.0 μg/mL serum) ranged from 5.6-9.6% CV. Possible interferences from other drugs which might be administered concurrently were studied. The method has been applied to the analysis of human serum samples.     

Rapid Analysis of Fluorine in Geological Samples with Ion Chromatographic Detection

Abstract

A method is described for the analysis of fluorine in geological samples involving the decomposition of the sample with phosphoric acid and the measurement of the fluoride ion concentration using an ion chromatograph. The detection limit is below 5 g F in the original sample. Multiple analyses of NBS-91 Opal Glass yielded a relative standard deviation of less than 2.5%. In excess of 30 samples can be analyzed in an 8 hour day. Potential interference from high carbon containing samples, such as oil shales, is discussed.     

Application of high resolution-ICP-MS (sector field-ICP-MS) to the fast and sensitive quality control of process chemicals in semiconductor manufacturing

For fast routine analysis of process chemicals used in semiconductor technology such as tetramethylammonium hydroxide (TMAH), ammonium fluoride/hydrofluoric acid mixtures, phosphoric, sulphuric or peroxodisulphuric acid (PDSA) low blanks are the paramount requirement for reliable sector field ICP-MS ultratrace analysis. When solutions containing a high amount of dissolved solids e.g. seawater samples have been analysed before, a thorough cleaning procedure and an adapted element menu is essential to lower the instrument blanks where possible or to achieve sufficient limits of detection (LoD) even at high blank levels. Due to its improved transmission and its ability to resolve spectral interferences inductively coupled plasma-sector field mass spectrometry is capable of detecting 1 ng/g of all metal impurities even K, Ca, and Fe in every matrix used for semiconductor production. LoDs range from < 1 to 30 pg/mL in diluted chemicals corresponding to 5 to 800 pg/mL in the original. This work describes the experiences with instrument cleaning and maintenance, sample preparation and introduction. The interface region between torch and lenses was seen to be the main source of blanks for elements such as Na. All sample manipulation has to be carried out under clean room conditions. The use of an inert sample introduction system (ISIS), platinum cones and at least medium resolution for elements between 24 and 80 amu creates a very robust method. High efficiency sample introduction systems such as USN and MCN have been studied alternatively.     

Gas chromatography with mass spectrometry for the quantification of ethylene glycol ethers in different household cleaning products

A rapid and simple procedure is reported for the determination of six ethylene glycol ethers in cleaning products and detergents using gas chromatography with mass spectrometry. The analytes were extracted from 2.0 g samples in acetonitrile (3 mL) and the extract was submitted to a clean‐up step by QuEChERS method, using a mixture containing 0.3 g magnesium sulfate, 0.15 g primary/secondary amine, and 0.05 g C₁₈. The clean acetonitrile extract (1 μL) was injected into the chromatographic system. No matrix effect was observed, so the quantification of the samples was carried out against external standards. Detection limits were in the range 3.0–27 ng/g for the six ethylene glycol ethers. The recoveries obtained, using the optimized procedure, were in the 89.4–118% range, with relative standard deviations lower than 14%. Twenty‐three different household cleaning products, including glass cleaner, degreaser, floor, softeners, and clothes and dishwashing detergents, were analyzed. Large interindividual variations were observed between samples and compounds.     

Large‐volume sample stacking with polarity switching for analysis of azo dyes in water samples by capillary electrophoresis

ABSTRACT

A simple, fast and efficient on-line pre-concentration method (large-volume sample stacking) by capillary electrophoresis was proposed for determination of azo dyes residues (allura red [AR], sunset yellow [SY] and tartrazine [TAR]) in water samples. Pre-concentration variables involved in the system were optimised using of a Box–Bhenken design. Under the optimal conditions: injection time 150.0 s, pre-concentration time 120.0 s and reverse potential ?8.0 kV, the proposed methodology improved the analytical sensibility achieving limits of detection of 21.0–41.4 µg L^?1 with enrichment factors of 82.1–210.8 fold. The large-volume sample stacking-capillary electrophoresis method was validated and applied to determine azo dyes residues in 20 water samples (bottled, spring and tap water). Two samples were positive for sunset yellow and tartrazine with a concentration of 25.3 and 30.2 µg L^?1 and % RSD less than 10.0% in all cases.     

Rapid dissolution of large environmental samples for the determination of fission products

The dissolution of large environmental samples was investigated using a microwave autoclave, capable of digestion conditions of 300 °C and 200 bar, for the application of rapid determination of radionuclides. Six samples of up to 5 g plant material were digested, also eliminating predigestion steps such as ashing and grinding. Batches of forty 1 g samples of plant leaves were also completely digested in 75 minutes. Quantitative recovery of ⁹⁰Sr from 5 g soil samples by leaching with 8M HNO₃ at 200 °C was achieved, whereas ¹³⁷Cs was not completely recovered from the large soil samples using total digestion or leaching (HCl:HNO₃) techniques, but quantitative recovery was achieved using fusion and sinter procedures.     

The Determination of a New Trifluorinated Quinolone,Fleroxacin, Its N-Demethyl,and N-Oxide Metabolites in Plasma and Urine by High Performance Liquid Chromatography with Fluorescence Detection

Abstract

A liquid chromatographic method is described for the determination of the new fluoroquinolone Ro 23–6240 and its N-demethyl and N-oxide metabolites in plasma and urine. The three substances were extracted from aqueous solution with dichloromethane/isopropanol containing sodium dodecyl sulphate. After evaporation and reconstitution, samples were analysed on a reversed-phase column using ion pair chromatography and fluorescence detection. The limit of quantification was 10–20 ng/ml (RSD 4%) using a 0.5 ml plasma sample, and the inter assay precision was 3–10% over the concentration range 50 ng/ml to 20 μg/ml. Recovery from plasma was 81% (RSD 10%) over the range 10 ng/ml to 5 μg/ml. The method has been applied successfully to the analysis of several thousand samples from human pharmacokinetic studies. Care has to be taken to avoid exposure of samples to direct sunlight, and the use of opaque vessels for sample storage and handling is recommended.     

Immunoassay for the Determination of 7-Hydroxycoumarin in Serum Using 'Real-Time' Biosensor Analysis

ABSTRACT

An inhibition immunoassay for the determination of total 7-hydroxycoumarin (7-OHC) in human serum samples using the BIACORE biosensor is described. 7-OHC-BSA was immobilised onto BIACORE sensor chips and 7-OHC was premixed with a polyclonal anti-7-OHC antibody and injected over this surface. Excess antibody bound to the immobilised conjugate, generating a binding response that was inversely proportional to the amount of 7-OHC in the sample. The sample buffer was formulated to minimise non-specific binding of serum components to the sensor surface. Regeneration of the sensor surface was optimised such that the conjugate-coated surface retained acceptable antibody-binding capacity over 64 binding-regeneration cycles. The recovery of free drug from samples spiked with 7-hydroxycoumarin-glucuronide (7-OHCG) approximated 100%, while the inter- and intra-day coefficients of variation for the assay were less than 8.76% for 5 replicates. The assay had a measuring range of 0.5 – 80 μg/ml. This BIACORE-based immunoassay for 7-OHC could be performed using crude samples and both the reproducibility and sensitivity compared well to established methods of analysis.     

Optimization of a radioanalytical procedure for the determination of uranium isotopes in environmental samples

A radiochemical procedure is described for the fast and sensitive measurement of uranium isotopes in gaseous and liquid effluents of nuclear facilities. Equally, this procedure is suitable to measure uranium isotopes in all kinds of environmental samples. Uranium is leached from ashed sample materials with HNO₃, HF, and Al(NO₃)₃ solution and separated from matrix elements by extraction with trioctylphosphinic oxide and backextraction with NH₄F. After radiochemical cleaning by coprecipitation with LaF₃ and anion exchange, uranium isotopes are electroplated on stainless steel discs from HCl/oxalate solution. The preparation is measured by alpha-spectrometry using surface barrier detectors. The detection limit for 1000 minutes of counting time is 2 mBq per sample and nuclide, the chemical yield is in the range of 50 to 80%.     

Effect of sample pre-treatment on the determination of steroid esters in hair of bovine calves

The effect of three sample pre-treatment steps, washing, cutting and grinding on the determination of steroid esters in hair is studied. The study is performed by using hair samples obtained after pour-on application of steroid esters to bovine calves. After sample pre-treatment the hair is treated with a mild reducing agent [tris(2-carboxyethyl)phosphine hydrochloride] to extract the steroid esters. After a solid-phase extraction clean-up step the extracts are analysed by using liquid chromatography combined with triple–quadrupole mass spectrometric detection. For the washing step the use of non-organic washing solvents like (warm) water and a solution of 0.1% sodium dodecyl phosphate and organic solutions containing different percentages of methanol are tested. By using the non-organic solvents and the organic solvents with a percentage of methanol <20% the recovery results are as good as the results obtained without washing the hair. Cutting the hair samples increases the analyte recoveries of incurred steroid esters by 20% compared to the non-cut hair. The analyte recoveries of cut hair samples are about 60–80% that of ground hair samples. The obtained surface expansion of hair samples by grinding proves to be necessary in order to achieve the highest possible analyte yields. Finally the use of pressurised liquid extraction (PLE) for the extraction of steroid esters from plain (no washing, cutting or grinding) hair is investigated. The first results show lower (up to 40%) extraction recoveries in comparison with the classical solvent extraction procedures. If the limit of detection requirement is met, PLE may be an alternative for extracting large numbers of hair samples due to the short sample treatment procedure involved.     

Pressurized liquid extraction using water/isopropanol coupled with solid-phase extraction cleanup for industrial and anthropogenic waste-indicator compounds in sediment

A broad range of organic compounds is recognized as environmentally relevant for their potential adverse effects on human and ecosystem health. This method was developed to better determine the distribution of 61 compounds that are typically associated with industrial and household waste as well as some that are toxic and known (or suspected) for endocrine-disrupting potential extracted from environmental sediment samples. Pressurized liquid extraction (PLE) coupled with solid-phase extraction (SPE) was used to reduce sample preparation time, reduce solvent consumption to one-fifth of that required using dichloromethane-based Soxhlet extraction, and to minimize background interferences for full scan GC/MS analysis. Recoveries from spiked Ottawa sand, commercially available topsoil, and environmental stream sediment, fortified at 4-720 μg per compound, averaged 76 ± 13%. Initial method detection limits for single-component compounds ranged from 12.5 to 520 μg/kg, based on 25 g samples. Results from 103 environmental sediment samples show that 36 out of 61 compounds (59%) were detected in at least one sample with concentrations ranging from 20 to 100,000 μg/kg. The most frequently detected compound, beta-sitosterol, a plant sterol, was detected in 87 of the 103 (84.5%) environmental samples with a concentration range 360-100,000 μg/kg. Results for a standard reference material using dichloromethane Soxhlet-based extraction are also compared.     

Preparation of functionalized magnetic nanoparticulate sorbents for rapid extraction of biphenolic pollutants from environmental samples

A new solid-phase extraction coupled with magnetic carrier technology was developed for extraction of bisphenol A (BPA) and diethylstilbestrol (DES) from water samples. The SPE sorbents, functionalized magnetic nanoparticles (Fe₃O₄@SiO₂/β-CD, core/shell), were synthesized in a two-stage system. The material was characterized by Fourier transform infrared spectroscopy, transmission electron microscopy, and a vibrating sample magnetometer. SPE extraction parameters, such as volume and pH of sample, adsorption time, and desorption conditions were optimized. Under selected conditions: 250 mL of water sample, 0.1 g of sorbents and elution with methanol (3 mL with 1% acetic acid), the extraction was completed in 25 min. SPE followed by HPLC was employed to determine BPA and DES in environmental samples. The developed method provided spiked recoveries of 80–105%, relative standard deviations of less than 7%, and LOD of BPA (20.0 ng/L) and DES (23.0 ng/L), respectively. The proposed method offered easy preparation of sorbents, rapid analysis, high enrichment yields, and reliable quantitative assay.