Validation of a simplified field-adapted procedure for routine determinations of methyl mercury at trace levels in natural water samples using species-specific isotope dilution mass spectrometry

A field-adapted procedure based on species-specific isotope dilution (SSID) methodology for trace-level determinations of methyl mercury (CH₃Hg⁺) in mire, fresh and sea water samples was developed, validated and applied in a field study. In the field study, mire water samples were filtered, standardised volumetrically with isotopically enriched CH₃²⁰⁰Hg⁺, and frozen on dry ice. The samples were derivatised in the laboratory without further pre-treatment using sodium tetraethyl borate (NaB(C₂H₅)₄) and the ethylated methyl mercury was purge-trapped on Tenax columns. The analyte was thermo-desorbed onto a GC-ICP-MS system for analysis. Investigations preceding field application of the method showed that when using SSID, for all tested matrices, identical results were obtained between samples that were freeze-preserved or analysed unpreserved. For DOC-rich samples (mire water) additional experiments showed no difference in CH₃Hg⁺ concentration between samples that were derivatised without pre-treatment or after liquid extraction. Extractions of samples for matrix–analyte separation prior to derivatisation are therefore not necessary. No formation of CH₃Hg⁺ was observed during sample storage and treatment when spiking samples with ¹⁹⁸Hg²⁺. Total uncertainty budgets for the field application of the method showed that for analyte concentrations higher than 1.5 pg g^–1 (as Hg) the relative expanded uncertainty (REU) was approximately 5% and dominated by the uncertainty in the isotope standard concentration. Below 0.5 pg g^–1 (as Hg), the REU was >10% and dominated by variations in the field blank. The uncertainty of the method is sufficiently low to accurately determine CH₃Hg⁺ concentrations at trace levels. The detection limit was determined to be 4 fg g^–1 (as Hg) based on replicate analyses of laboratory blanks. The described procedure is reliable, considerably faster and simplified compared to non-SSID methods and thereby very suitable for routine applications of CH₃Hg⁺ speciation analysis in a wide range of water samples.     

Validation of a tentative microsatellite marker for the dopamine D4 receptor gene by capillary gel electrophoresis

Two to four-basepair-short tandem repeats (i.e. microsatellites) are broadly utilized as genetic markers for mapping disease loci in whole genome search analyses. Based on their close vicinity on chromosome 11, the D11S1984 microsatellite was anticipated as a tentative marker for the dopamine D4 receptor gene. A capillary gel electrophoresis based genotype analysis method and an in-house made computational tool was developed for the analysis of the D11S1984 microsatellite marker to examine a healthy Hungarian population of n=106. The data obtained did not suggest significant linkage between the D11S1984 marker and the DRD4 gene.     

Determination of pyridine in soil and water samples of a polluted area

A method for the analyses of pyridine in environmental samples is described. For soil samples a distillation procedure followed by an extraction, an acidic extraction or a Soxhlet extraction can be used. For water samples a distillation procedure followed by extraction can be employed. Deuterated pyridine is used as an internal standard and the extracts are analyzed by GC-MS. The recoveries of the methods are higher than 80%; the detection limits for pyridine are 0.01 mg/kg for soil samples and 0.2 g/l for water samples.     

Magnetite surface area titration using nitric oxide, II. Pretreatment effects and silica-supported samples

The use of NO adsorption for determination of Fe₃O₄ surface areas has been examined and extended, from earlier work on unsupported samples, to silica-supported Fe₃O₄. Gravimetric studies confirm earlier suggestions that the irreversible NO adsorption uptake on unsupported Fe₃O₄ is dependent upon sample pretreatment. Long (ca. 24 h) vacuum treatment at 650 K leads to increased apparent NO adsorption uptakes due to reduction of the surface. Magnetite particle size estimates were made using irreversible NO adsorption uptakes on silica-supported Fe₃O₄ samples that had received a standard 1 h vacuum pretreatment at 650 K. These estimates agreed well with average particle sizes calculated using x-ray line-broadening and magnetization measurements, indicating that NO adsorption can, in fact, be used to measure magnetite surface areas on silica-supported samples.

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Camille and Henry Dreyfus Foundation Teacher-Scholar; to whom all correspondence should be addressed.     

Identification of a new degradation product of the antifouling agent irgarol 1051 in natural samples

A main degradation product of Irgarol [2-(methylthio)-4-(tert-butylamino)-6-(cyclopropylamino)-s-triazine], one of the most widely used compounds in antifouling paints, was detected at trace levels in seawater and sediment samples collected from several marinas on the Mediterranean coast. This degradation product was identified as 2-methylthio-4-tert-butylamino-s-triazine. The unequivocal identification of this compound in seawater samples was carried out by solid-phase extraction (SPE) coupled on-line with liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (LC-APCI-MS). SPE was carried out by passing 150 ml of seawater sample through a cartridge containing a polymeric phase (PLRP-s), with recoveries ranging from 92 to 108% (n=5). Using LC-MS detection in positive ion mode, useful structural information was obtained by increasing the fragmentor voltage, thus permitting the unequivocal identification of this compound in natural samples. Method detection limits were in the range of 0.002 to 0.005 microg/l. Overall, the combination of on-line SPE and LC-APCI-MS represents an important advance in environmental analysis of herbicide degradation products in seawater, since it demonstrates that trace amounts of new polar metabolites may be determined rapidly. This paper reports the LC-MS identification of the main degradation product of Irgarol in seawater and sediment samples.     

Round-robins in the area of uranium and plutonium bulk analysis of environmental samples

In the framework of a collaboration between laboratories involved in bulk U and Pu analysis of environmental samples (DIF centre of the French Commissariat à l’Energie Atomique, US National Laboratories of New Brunswick, Lawrence Livermore, Pacific Northwest, Oak Ridge, and Los Alamos), two round-robins were organised, each one consisting of the complete analysis (chemical preparation and isotope measurement) of three Quality Control samples. The samples were 10 × 10 cm cotton tissues (“swipe samples”) containing low amounts of U (from ~20 to ~150 ng) and Pu (from ~0.15 to ~10 pg). Despite using different spikes, different methods of sample preparation and different analytical instrumentation, the results for U and Pu contents and isotopic compositions reported by all laboratories are globally in good agreement. All laboratories are able to measure sub-pg amounts of U and Pu isotopes with acceptable accuracy and reproducibility, even if limited discrepancies are observed affecting one or other measurement and/or laboratory. General and laboratory specific recommendations were discussed and adopted to continue to improve the accuracy and precision of the measurements.     

Voltammetric probe of milk samples by using a platinum microelectrode

Milk is a complex heterogeneous fluid containing many components in several states of dispersion. When used as a bulk solvent for studying electrochemical processes of some of the electroactive species present, it displayed mainly aqueous solution properties. With microelectrodes (25 μm in diameter) some typical constituents can be detected and the reproducibility of the processes studied was found to be satisfactory, with relative standard deviations (r.s.d.s.) lower than 2%, whereas measurements with conventional-sized platinum electrode (3 mm in diameter) gave r.s.d.s, of about 10%. Moreover, because of enhanced mass transport associated with the smallest electrodes, it was possible to diagnose the formation of precipitates of calcium phosphates on the electrode surface, as a consequence of a CEC electrode process at ?0.920 V vs. SCE, involving protons released by H₂PO^?₄, HPO^2?₄ formed in the electrode reaction and Ca²⁺. The reduction of acidic groups from casein, the oxidation of ascorbate and oxygen effects were also studied.     

Analysis of solid uranium samples using a small mass spectrometer

A mass spectrometer for isotopic analysis of solid uranium samples has been constructed and evaluated. This system employs the fluorinating agent chlorine trifluoride (ClF₃) to convert solid uranium samples into their volatile uranium hexafluorides (UF₆). The majority of unwanted gaseous byproducts and remaining ClF₃ are removed from the sample vessel by condensing the UF₆ and then pumping away the unwanted gases. The UF₆ gas is then introduced into a quadrupole mass spectrometer and ionized by electron impact ionization. The doubly charged bare metal uranium ion (U²⁺) is used to determine the U²³⁵/U²³⁸ isotopic ratio. Precision and accuracy for several isotopic standards were found to be better than 12%, without further calibration of the system. The analysis can be completed in 25 min from sample loading, to UF₆ reaction, to mass spectral analysis. The method is amenable to uranium solid matrices, and other actinides.     

Determination of radiostrontium in soil samples using a crown ether

A simple and rapid method has been developed for the separation and determination of total radiostrontium in soil. The method consists of three basic steps: oxalate precipitation to remove bulk potassium, chromatographic separation of strontium from most inactive and radioactive interferences utilizing a crown ether (Sr. Spec, EIChroM Industries, Il. USA) and oxalate precipitation of strontium to evaluate the chemical yield. Radiostrontium is then determined by liquid scintillation counting of the dissolved precipitate. When 10 g samples of soil are used, the sensitivity of the method is about 10 Bq/kg. The chemical yield is about 80%. The separation and determination of radiostrontium can be carried out in about 8 hours.     

Selective catch and release of a synthetically useful phosphine ligand

The selective catch and release of the synthetically useful (o-biphenyl)(t-butyl)₂P from basic and non basic compounds, utilizing solid phase supported sulfonic acid sources is demonstrated.     

Identification and structural characterization of febuxostat metabolites in rat serum and urine samples using UHPLC–QTOF/MS

Febuxostat is a novel nonpurine type of highly selective xanthine oxidoreductase inhibitor. A rapid and sensitive ultra‐high‐performance liquid chromatography–quadrupole time‐of‐flight mass spectrometry method for simultaneous separation and determination of febuxostat and its metabolites in rat serum and urine was developed at various time points after oral administration to the rats. The febuxostat metabolites were predicted by biotransformation software and transformed to a personal compound database to quickly determine the possible metabolites from the MS1 data. The possibility of the MS/MS fragmentation was calculated by the Molecular Structure Correlator software. As a result, five phase I and two phase II metabolites in rat serum, and seven phase I and three phase II metabolites in rat urine were identified, of which four metabolites (M2, M5, M6, M7) have not been reported before. The metabolite toxicities are predicted, and the results are helpful for the design of new xanthine oxidoreductase inhibitors.     

Determination of copper in urine and water samples using a simple led-based colorimeter

A cheap and simple colorimetric assay based on the reaction with sodium 8-aminoquinoline-5-azobenzene-4′-sulfonate (SPAQ) is applied to the determination of copper in urine and water samples. The proposed technique employs a light emitting diode (LED) as a light source and a cheap common light dependent resistor (LDR) as a detector. This device functions on the basis of the level of light received by photoresistor (LDR), which is connected to a digit multimeter yielding resistance readings increasing with the increase in light absorption by sample solution. Experimental variables affecting the complex formation were optimized applying the Taguchi method. Under the optimum conditions, calibration plot was linear in the analyte concentration range of 0.1–2 μg/mL. The stoichiometry of metal/ligand ratio, the stability constant, and molar absorptivity (ɛ) of Cu(II)-SPAQ complex were also found. The relative standard deviation for five replicate determinations of 1 μg/mL Cu(II) was 3.64% and the corresponding limit of detection was 35 μg/L.     

Investigation of the appropriateness of using ethoxychelerythrine as a representative quality marker of Zanthoxylum nitidum

JPC – Journal of Planar Chromatography – Modern TLC - Quaternary benzo[c]phenanthridine alkaloids (QBAs), such as chelerythrine (CHE) and nitidine (NIT), represent the important...     

Separation of zinc from aqueous samples using a molecular imprinting technique

In this article, the separation of zinc from aqueous samples by solid-phase extraction based on a molecular imprinting technique is described. Zn-imprinted polymer was prepared by free radical solution polymerisation in a glass tube containing ZnSO₄, morin, 4-vinylpyridine as a functional monomer, ethyleneglycoldimethacrylate as a cross-linking monomer, and 2,2′-azobisisobutyronitrile as an initiator. The obtained polymer block was ground and sieved (55–75 µm) and the Zn–morin complex was separated from polymer particles by leaching with 2M HCl. The synthesised polymer particles have been characterised by IR and differential scanning calorimetric studies either before or after leaching. The effects of different parameters, such as pH, adsorption and desorption time, type and minimum amount of the eluent for elution of the complex from polymer were evaluated. Extraction efficiency more than 99% was obtained by elution of the polymers with 10 mL of CH₂Cl₂–dimethyl sulfoxide (1 : 1, v/v). The detection limit of the proposed method was 2.9 µg L^?1. A dynamic linear range in the range of 25–200 µg L^?1 was obtained. The relative standard deviation was found to be below 9.2%. In addition, the influence of various cationic and anionic interferences on the complex recovery was studied. The method was applied to the recovery and determination of Zn in a few different real samples.     

Assessment of pesticide contamination in soil samples from an intensive horticulture area, using ultrasonic extraction and gas chromatography-mass spectrometry

In order to reduce the amount of sample to be collected and the time consumed in the analytical process, a broad range of analytes should be preferably considered in the same analytical procedure. A suitable methodology for pesticide residue analysis in soil samples was developed based on ultrasonic extraction (USE) and gas chromatography–mass spectrometry (GC–MS). For this study, different classes of pesticides were selected, both recent and old persistent molecules: parent compounds and degradation products, namely organochlorine, organophosphorous and pyrethroid insecticides, triazine and acetanilide herbicides and other miscellaneous pesticides. Pesticide residues could be detected in the low- to sub-ppb range (0.05–7.0 μg kg⁻¹) with good precision (7.5–20.5%, average 13.7% R.S.D.) and extraction efficiency (69–118%, average 88%) for the great majority of analytes. This methodology has been applied in a monitoring program of soil samples from an intensive horticulture area in Póvoa de Varzim, North of Portugal. The pesticides detected in four sampling programs (2001/2002) were the following: lindane, dieldrin, endosulfan, endosulfan sulfate, 4,4′-DDE, 4,4′-DDD, atrazine, desethylatrazine, alachlor, dimethoate, chlorpyrifos, pendimethalin, procymidone and chlorfenvinphos. Pesticide contamination was investigated at three depths and in different soil and crop types to assess the influence of soil characteristics and trends over time.     

An effective and economical method for the storage of plasma samples using a novel freeze-drying device

Biological samples, especially plasma samples, are conventionally stored under freezing conditions to maintain sample integrity prior to the detections of analytes. However, the storage of samples in a low-temperature environment is electric energy consuming, and the preparation of samples prior to analytes detection may be complicated. In this work, an effective and economical method was proposed to freeze-dry the samples using a novel device to allow subsequent storage of samples at ambient temperature. The sample preparations integrated in the new method are simple and easy to follow. Analytes were directly extracted with the extraction agent before sample injections. This new method was validated with quality control (QC) samples of levetiracetam and mycophenolic acid (MPA), and it was also applied to the pharmacokinetic (PK) studies of both drugs in healthy volunteers. When QC samples were stored and prepared with the new method, the detections of analytes were accurate and repeatable, and the analytes maintained stability for a long time. The PK studies of levetiracetam and MPA in healthy volunteers showed that the PK parameters of analytes stored with the new method were consistent with those stored with the conventional method. In conclusion, this effective and economical method is a practical option in reality and can play a big role in clinical and scientific drug researches.     

Studies of phosphate anion sorption using the soil samples

The paper presents the results of studies of phosphate anion sorption on various types of soil taken up from the Lublin Province (Poland). Anions belong to the group of ions witch undergo insignificant sorption according to the soil science. As follows from the studies anion sorption depends insignificantly on pH. Sorption isotherms can be described using the Freundlich equation. Sorption extent depends on concentration of iron ions and organic substances in the sample. Specific sorption (chemisorptions) plays the greatest role in the process under investigation.