Biomedical subjects

M C Hennion

Publications and source records attributed to M C Hennion.

17 recordsLinked to original sources

PubMed2001

Picogram determination of "earthly-musty" odorous compounds in water using modified closed loop stripping analysis and large volume injection GC/MS.

"Earthy-musty" off-flavor problems in water samples are due to organic compounds present at the sub-part-per-trillion level. Numerous analytical methods such as purge and trap, liquid/liquid extraction, and closed-loop stripping analysis (CLSA) followed by GC/MS analysis have been used to determine these compounds. However, these methods offer poor sensitivity (detection limits of approximately 1 to 10 ng/L) when compared to the 20-30 pg/L of sensorial sensitivity. The purpose of this study was to develop a new method involving a modified CLSA preconcentration technique together with large volume injection GC/MS in order to attain analytical sensitivity equal to or better than olfactory sensitivity. For eight target compounds that cause taste and odor problems in water at trace levels, the method developed was linear in the 0.05-10 ng/L range and provided recoveries greater than 70% together with satisfactory repeatability. Detection limits as low as 15-30 pg/L were achieved, representing a 50-fold improvement in sensitivity as compared to current methods. The accuracy and sensitivity of the method were demonstrated in different aqueous matrixes, including raw surface water. The method was successfully applied to earthy-musty water samples that had remained unsolved by conventional techniques, thus proving its effectiveness.

Journal Article↗

PubMed2000

Immunoaffinity solid-phase extraction for the trace-analysis of low-molecular-mass analytes in complex sample matrices.

Immunoaffinity solid-phase extraction (SPE) sorbents, so-called immunosorbents (ISs), are based upon molecular recognition using antibodies. Thanks to the high affinity and high selectivity of the antigen-antibody interaction, they allow a high degree of molecular selectivity and have shown to be a unique tool in the sample preparation area these last few years. Extraction and clean-up of complex biological and environmental aqueous samples are achieved in the same step and from large volumes when required. Their application to extracts from solid matrixes is solvent-free and more simple than any other clean-up procedure. Single analytes can be targeted, but since an antibody can also bind one or more analytes having structure similar to the one used for its preparation, ISs have been developed for targeting a single analyte and its metabolites. The cross-reactivity was also exploited for developing ISs that could selectively extract a whole class of structurally related compounds. This review describes the current technology used for the synthesis of the ISs, their properties and their field of application. The different parameters governing the antigen-antibody interactions and the solid-phase extraction process are discussed. Emphasis is given to the optimisation of the SPE sequence, especially to the desorption and regeneration steps. The importance of the capacity and its relationship with the analytes recovery and breakthrough volumes is highlighted for class-specific ISs. Multi-class-selective ISs are also presented. Validation studies are reviewed using various certified reference materials. Relevant examples, involving combination with chromatography in both off-line and on-line mode, illustrate the high selectivity provided in various complex matrixes. Miniaturisation is also described, since it allows high throughput of samples.

Animals↗

PubMed2000

Graphitized carbons for solid-phase extraction.

The objective of this review is to provide updated information about the most important features of graphitized carbonaceous sorbents used for solid-phase extraction (SPE) of organic compounds from liquid natural matrices or extracts. The surface characteristics of graphitized carbon blacks and porous graphitic carbons are described which are responsible for the various types interactions (hydrophobic, electronic and ion-exchange) with analytes. The method development is given which is based on the prediction from liquid chromatographic retention data obtained using porous graphitic carbon. Emphasis is placed on their capability for trapping very polar and water-soluble analytes from aqueous samples. Comparison is made between carbon-based SPE sorbents and other reversed-phase materials such as octadecyl silicas and highly cross-linked copolymers. Especially, the difficulty encountered for the desorption of some strongly retained analytes is explained by LC data and solutions are given for optimizing the composition and volume of the desorption solution. Many examples illustrate the various common features of graphitized carbons which are the extraction of very polar analytes and multiresidue extractions. Some applications are specific to graphitized carbon black due to the presence of surface functional groups. They include the extraction of anionic compounds such as benzene and naphthalene sulfonates or acidic pesticides. Other applications are specific to porous graphitic carbon due to its flat and homogeneous surface. One example is the trace extraction of coplanar polychlorinated biphenyls (PCBs), dibenzo-p-dioxins and dibenzofurans from other PCB congeners.

Chromatography, Liquid↗

PubMed1999

Selective immunoclean-up followed by liquid or gas chromatography for the monitoring of polycyclic aromatic hydrocarbons in urban waste water and sewage sludges used for soil amendment.

A selective clean-up procedure using immunoaffinity solid-phase extraction was applied for the trace-level determination of polycyclic aromatic hydrocarbons (PAHs) in urban waste water and sewage sludges used for soil amendment. Anti-pyrene antibodies have been immobilized on a silica-based sorbent and the cross-reactivity of the antibodies towards structurally related compounds were allowed to extract the whole class of priority PAHs. The selectivity of the antibodies provided clean extracts from sludges and, therefore, the identification and quantification were shown to be easier using either liquid chromatography (LC) with UV diode array and fluorescence detection in series or gas chromatography-mass spectrometry (GC-MS), although some loss of up to 50% was observed for the clean-up. The identification of the PAHs by matching of UV and MS spectra was greatly improved. The procedure, including immunoclean-up and LC coupled to diode array and fluorescence detection, was validated using certified reference materials with native PAHs of concentrations in the range of 0.57-2.16 mg/kg (dry sludges).

Chromatography, Gas↗

PubMed1999

Solid-phase extraction: method development, sorbents, and coupling with liquid chromatography.

The objective of this review is to provide updated information about the most important features of the new solid-phase extraction (SPE) materials, their interaction mode and their potential for modern SPE. First, the recent developments are given in formats, phases, automation, high throughput purpose and set-up of new types of procedures. Emphasis is then placed on the large choice of sorbents for trapping analytes over a wide range of polarities, such as highly cross-linked copolymers, functionalized copolymers, graphitized carbons or some specific n-alkylsilicas. The method development is given which is based on prediction from liquid chromatographic retention data or solvation parameters in order to determine the main parameters of any sequence (type and amount of sorbent, sample volume which can be applied without loss of recovery, composition and volume of the clean-up solution, composition and volume of the desorption solution). Obtaining extracts free from matrix interferences in a few steps--one step when possible--is now included in the development of SPE procedure. New selective phases such as mixed-mode and restricted access matrix sorbents or emerging phases such as immunosorbents or molecularly imprinted polymers are reviewed. Selectivity obtained by combining two sorbents is described with the use of ion-exchange or ion-pair sorbents. Special attention is given to complete automation of the SPE sequence with its on-line coupling with liquid chromatography followed by various detection modes. This represents a fast, modern and reliable approach to trace analysis. Many examples illustrate the various features of modern SPE which are discussed in this review. They have been selected in both biological and environmental areas.

Chromatography, Liquid↗

PubMed1999

Selective on-line immunoextraction coupled to liquid chromatography for the trace determination of benzidine, congeners and related azo dyes in surface water and industrial effluents.

A new extraction immunosorbent involving antigen-antibody interactions was coupled on-line to liquid chromatography for the selective extraction in aqueous samples of benzidine and congeners, widely used as intermediate compounds in the manufacturing of dyes and pigments. Due to the cross-reactivity of the antibodies for analytes with chemical structures closely related to that of the analyte used for immunization, the immunoextraction sorbent was shown to be able to extract aminoazobenzene and related azo dyes with good recoveries. The on-line coupling was optimized for the trace determination of benzidine, dichlorobenzidine, aminoazobenzene and some azo dyes with detection limits in the range 0.1 to 1 microgram/l. The high selectivity of the immunoextraction was shown by comparing the analysis of an industrial textile effluent obtained using precolumns packed either with a non-selective polymeric sorbent or with the anti-benzidine immunosorbent. In such complex samples, extraction and clean-up are achieved in the same step.

Azo Compounds↗

PubMed1998

Isolation of priority polycyclic aromatic hydrocarbons from natural sediments and sludge reference materials by an anti-fluorene immunosorbent followed by liquid chromatography and diode array detection.

The selective isolation of PAHs from complex environmental mixtures was accomplished by means of a new methodology based on antigen--antibody interactions. This method consists on the extraction of PAHs from water samples onto an anti-fluorene immunosorbent (IS) followed by liquid chromatography with diode array detection. Environmental sediments and a sludge reference material containing PAHs were analyzed using this methodology in order to validate the performance of the IS for the cleanup procedure of such materials. Sediments were extracted by sonication with dichloromethane/methanol (2:1), and the extracts were brought to a volume of 100 mL of water in order to perform the extraction with the anti-fluorene IS. The reliability of the cleanup achieved by the IS was well demonstrated in the analysis of sediment and sludge complex samples containing the priority PAHs established by the U.S. EPA at concentrations varying from 56 micrograms/kg to 26 mg/kg. Results were compared to those obtained with conventional cleanup procedures showing a better selectivity for PAHs. The chromatograms presented a clear baseline allowing the determination and quantification of PAHs at the ppb level. Using immunosorbents, extraction, trace enrichment, and cleanup were accomplished in only one step.

Chromatography, Liquid↗

PubMed1998

Optimization and validation of solvent and supercritical-fluid extractions for the trace-determination of polycyclic aromatic hydrocarbons in sewage sludges by liquid chromatography coupled to diode-array and fluorescence detection.

There is a need for a better characterization of sludges from wastewater treatment plants which are destined to be spread on agricultural land. Inorganic pollutants are regularly controlled, but organic pollutants have received little attention up to now. The main problem for trace analysis of organic pollutants comes from the complexity of the various matrices of sludges, which depends on their origins. Therefore, methods described for soils and sediments cannot be directly applied to sludges which contain high amount of lipids. This paper provides a method for trace-determination of polycyclic aromatic hydrocarbons in the range of mg/kg of dried sludge including an extraction step, and an analysis step by liquid chromatography with fluorescence detection for sensitive quantification and UV-diode-array detection for confirmation. The extraction step was optimized by a selection of the solvent used for both Soxhlet and supercritical-fluid extraction and by setting the experimental conditions (temperature, pressure, modifier, etc.) used for SFE. Extraction recoveries were found similar and quantitative for the two procedures. However supercritical-fluid extraction appears to be a good alternative to Soxhlet extraction because of the consumption of less time and solvent. Detection limits were obtained in the range of 0.1-1 mg/kg of dried sludges, with possible confirmation by UV spectra. The whole method (extraction/quantification/confirmation) was validated using sludges which have been certified by the Community Bureau of Reference from Brussels (CRM No. 088). Application to the determination of PAHs in urban sludges is presented.

Chromatography, Liquid↗

PubMed1998

Determination of some physicochemical parameters of microcystins (cyanobacterial toxins) and trace level analysis in environmental samples using liquid chromatography.

Some physicochemical parameters of three microcystin standards, known to be potent hepatotoxins produced by cyanobacteria, were determined using well defined chromatographic measurements. The logarithm of their retention factor on octadecylsilica (ODS) with water as the eluent, which is an estimation of the hydrophobicity of a molecule, was assessed at pH 7 at 3.9, 4.2 and 4.4 for microcystins-YR, -LR and -RR, respectively. Though being rather hydrophobic, microcystins also possess polar functions, namely carboxylic acids, amino and amido groups. The ionization of carboxylic groups occurs at pH values of 3.3-3.4. In environmental waters, microcystins are neutral or anionic. They are readily soluble in water, the solubility of microcystin-LR being higher than 1 g/l. Owing to their hydrophobicity and their polar functions, microcystins remain in the aqueous phase rather than being adsorbed on sediments or on suspended particulate matter. In a river water spiked with microcystins at 5 micrograms/l, only 10% was adsorbed on particles and 7% on the sandy sediment after three days. A method using solid-phase extraction on ODS followed by high-performance--or micro--liquid chromatography was optimized to detect microcystins at trace level in water. A clean-up was introduced to eliminate part of the interfering compounds coextracted during the sample percolation. Good recoveries (75-80%) were obtained. The method was linear, reproducible (with relative standard deviations ranging from 5 to 8%) and enabled the determination of microcystins at levels as low as 30 ng/l in drinking water and 100-200 ng/l in surface waters. The production of toxins by two strains of cyanobacteria was evaluated. Variations in the microcystin-LR content in the cells and in the medium of Microcystis aeruginosa PCC7806 were recorded over a five-week period. Toxin production was not correlated to the biomass but depended on the growth stage and was maximal at the end of the exponential growth phase. The release of toxin in water occurred essentially in old cultures where microcystin-LR was determined at concentrations of 170 and 280 micrograms/l in the media of M. aeruginosa PCC7806 and M. aeruginosa PCC7813, respectively. Other microcystins are likely to be synthesized by these strains. But owing to the lack of standards, mass spectrometric detection is required for further identification. This study points out the need of having other standards for water quality monitoring.

Chromatography, High Pressure Liquid↗

PubMed1998

Multiresidue analysis of pesticides using new laminar extraction disks and liquid chromatography and application to the French priority list.

The national French lists of priority pesticides to be monitored in drinking and/or surface water contain various pesticides with a wide range of physico-chemical properties and can be modified on a regional scale with the addition of other pesticides, depending on local agricultural usage. A multiresidue extraction method is presented using new disk formats engineered for high throughput that are particularly well adapted to the extraction of compounds from high volumes of dirty samples. However, because of the occurrence of very polar and very apolar compounds in the lists, two procedures are required for the extraction step. Divinylbenzene disks were used to extract the more polar compounds, as well as the moderately polar or acidic ones. For apolar pesticides, a C18 silica disk was used, and 10% methanol was added to the water sample before percolation in order to avoid adsorption on the flasks and connecting tubes. Since 1 l of surface water is extracted in less than 5 min without previous filtration using these new laminar disks, the percolation time is no longer a limiting factor in the analysis scheme of surface water samples containing suspended matter. The sample volume can be easily increased in order to reach lower detection limits, provided that the extraction conditions have been optimized in order to minimize the amount of co-extracted and interfering substances. A considerable decrease in the effect of the humic and fulvic substances was achieved using divinylbenzene disks, which allows the samples to be handled at pH 6, for the polar pesticides. Moreover, the necessary addition of 10% methanol in the samples for the extraction of the apolar ones also considerably decreases the amount of co-extracted analytes. The time of the whole sample preparation sequence, i.e., conditioning of the disks, sample extraction, sample clean-up and desorption, is achieved within 10 min for six simultaneous samples. Detection limits in the range 0.01-0.05 microgram l-1 are easily obtained for most pesticides contained in the national lists from 1 l of real surface water samples. The two procedures described in this work allow the handling of any compounds having a water-octanol constant, log Kow, in the range 1-6.

Chromatography, Liquid↗

PubMed1998

Effect of the various parameters governing solid-phase microextraction for the trace-determination of pesticides in water.

The parameters governing solid-phase microextraction (SPME) are investigated, with emphasis on the determination of the partition coefficients, K, and their use to predict the selection of a fibre, depending on the respective characteristics of the fibres and the analytes. Film thickness and stability of the compounds can interfere with the determination of K values. The time profile curves were determined for twelve pesticides having a wide range of water solubilities and polarities and using four fibres (polydimethylsiloxane, polydimethylsiloxane-divinylbenzene, Carbowax-divinylbenzene and polyacrylate). Although the affinity order was different for the four coatings, no correlation was found between the respective characteristics of the fibres and solutes. The two fibres containing divinylbenzene were shown to have the highest affinities and the polydimethylsiloxane had the lowest affinity. The polyacrylate fibre which is the more polar commercial fibre did not provide the highest affinities for the more polar and water-soluble analytes. The important parameters for quantitative analysis have been evaluated. The calibration curves were similar when one analyte of interest was present on its own in a drinking water sample, or when eleven other pesticides were present at the same concentration or when much higher concentrations of other analytes were present in the sample. Linearity was obtained over a wide range of concentrations in drinking water samples. Detection limits are in agreement with European regulatory levels in drinking water for most of the analytes using solid-phase microextraction-gas chromatography-nitrogen-phosphorus detection (SPME-GC-NPD). In contaminated surface water samples, the chromatograms are relatively clean and most of the compounds can be detected at levels lower than 0.5 microgram/l.

Calibration↗

PubMed1997

Determination of okadaic acid by micellar electrokinetic chromatography with ultraviolet detection.

Micellar electrokinetic chromatography (MEKC) with ultraviolet (UV) detection was applied for the determination of non-derivatized phycotoxins associated with diarrhoetic shellfish poisoning. A detection limit for 40 pg of okadaic acid (OA) was achieved. The UV intensities of this toxin measured at 200 nm showed good linearity in the range 40-640 pg. OA was detected in mussels spiked with 10 ng/g whole tissue. The presence of OA and dinophysistoxin-2 was observed in the crude extract of the dinoflagellate Prorocentrum lima.

Animals↗

PubMed1997

A new method for determination of maitotoxin by capillary zone electrophoresis with ultraviolet detection.

Capillary zone electrophoresis with UV detection was applied to the rapid and efficient separation of an underivatized phycotoxin, maitotoxin, associated with ciguateric fish poisoning. Highly sensitive detection was obtained by UV absorption at 195 nm. A detection limit of 50 pg of maitotoxin was achieved at this wavelength. Analysis involved using a fused silica capillary coated with a hydrophobic phase, polyvinylalcohols. Confirmation of the electrophoretic peak of maitotoxin was further evaluated by cytotoxicity on a mammalian fibroblastic cell line, BHK 21 C13.

Animals↗

PubMed1997

[Determination of phycotoxins in aquatic medium by capillary electrophoresis].

Marine phycotoxins present a major public health problem due to their ability to contaminate seafoods. Toxic phytoplankton is not limited, however, to the coastal areas in Europe. There are more and more problems in freshwater reservoirs, in lakes, and in ponds from which grazing animals get their water. Okadaic acid (OA), a polyether toxin from the marine dinoflagellate, Prorocentrum lima, and microcystins (MCYSTs), a potent hepatotoxic cyclic heptapeptides produced by many strains of cyanobacteria have been shown to be a powerful tumor promotor. Thus, considerable effort has been undertaken to find sensitive and easy detection techniques for the determination of phycotoxins from various matrices (microalgae, freshwater, mussels, fish, ...). Different biological and chemical methods have been developed to identify these toxins in shellfish and fish. The mouse bioassay method has been widely used for the detection of toxins such as maitotoxin and ciguatoxin, which are not easily identified by chemical procedures. In this report we describe a capillary electrophoretic method that enables us to detect okadaic acid, microcystins (MCYST-YR, MCYST-LR, MCYST-RR) and maitotoxin in picogram range.

Animals↗

PubMed1996

Detection of cyanobacterial toxins (microcystins) in cell extracts by micellar electrokinetic chromatography.

A micellar electrokinetic chromatography (MEKC) method with UV detection is described for the rapid and efficient separation of three microcystins: microcystin-YR (MCYST-YR), microcystin-LR (MCYST-LR) and microcystin-RR (MCYST-RR). A detection limit of 7.5 pg for each toxin was achieved. The UV intensities of these toxins measured at 200 nm showed good linearity in the range 7.5-150 pg. The production of MCYST-LR in three cultured strains of cyanobacteria, namely Microcystis aeruginosa strain IP7806, Microcystis aeruginosa strain IP7813 and Oscillatoria agardhii strain IP7805, was evaluated.

Bacterial Toxins↗

PubMed1993

Determination of carbaryl and some organophosphorus pesticides in drinking water using on-line liquid chromatographic preconcentration techniques.

Reversed-phase high-performance liquid chromatography (HPLC) was adapted for the determination of trace concentrations of carbaryl and seven organophosphorus pesticides in drinking water. Between 100 and 300 ml of water sample is passed through a 1.5-cm precolumn, packed with C18-bonded silica or styrene-divinylbenzene copolymer (PRP-1) sorbent at a flow-rate of 3 ml/min. The HPLC system is then switched to an acetonitrile-water gradient elution programme. The analytes that have been concentrated on the precolumn are eluted and separated on a 15-cm C18 analytical column and are determined by measuring their UV absorption at 254 nm. This wavelength was selected as the optimum for the simultaneous determination of these pesticides. The preconcentration yields of the examined solutes obtained with the two types of precolumn are almost identical. Band broadening is avoided by a suitable choice of the C18 precolumn and the analytical column. With 200 ml of tap water, the recoveries for most of the examined pesticides were ca. 90%, except for carbaryl (54%). The detection limits are in the range 0.03-0.2 micrograms/l.

Carbaryl↗

PubMed1993

Determination of phenoxyacid herbicides in drinking water at the ppt-level by liquid chromatography and on-line selective preconcentration.

On-line precolumn sample handling using an anion-exchanger is applied to preconcentrate phenoxyacid herbicides in aqueous samples prior to their LC separation. Since direct percolation of large sample volumes through the ion-exchanger has to be avoided owing to the high content of inorganic anions in natural waters, a two-step preconcentration is carried out: phenoxyacids are concentrated in their neutral (acidic) form by percolation of natural samples at pH 1 first through a precolumn packed with the copolymer-based PRP-1 sorbent. Then, the PRP-1 precolumn is coupled on-line with a second one packed with the anion-exchanger and 3 ml of deionised water with 35% of acetonitrile allows the phenoxyacids to be desorbed from the PRP-1 sorbent and reconcentrated on the anion-exchanger in their ionic form. The content of the anion-exchanger is analysed on-line by coupling with a C18 analytical column and elution is made with a water-acetonitrile gradient. Detection limits in drinking water from a 500-ml sample are between 15 and 35 ng/l (ppt) and identity of phenoxyacids is reinforced by the fact that analytes are preconcentrated by the anion-exchanger. This methodology can be fully automated.

2,4-Dichlorophenoxyacetic Acid↗