water-column Dotaz Zobrazit nápovědu
In this work, the applicability of Sequential Injection Chromatography for the determination of transition metals in water is evaluated for the separation of copper(II), zinc(II), and iron(II) cations. Separations were performed using a Dionex IonPAC™ guard column (50mm×2mm i.d., 9 µm). Mobile phase composition and post-column reaction were optimized by modified SIMPLEX method with subsequent study of the concentration of each component. The mobile phase consisted of 2,6-pyridinedicarboxylic acid as analyte-selective compound, sodium sulfate, and formic acid/sodium formate buffer. Post-column addition of 4-(2-pyridylazo)resorcinol was carried out for spectrophotometric detection of the analytes׳ complexes at 530nm. Approaches to achieve higher robustness, baseline stability, and detection sensitivity by on-column stacking of the analytes and initial gradient implementation as well as air-cushion pressure damping for post-column reagent addition were studied. The method allowed the rapid separation of copper(II), zinc(II), and iron(II) within 6.5min including pump refilling and aspiration of sample and 1mmol HNO3 for analyte stacking on the separation column. High sensitivity was achieved applying an injection volume of up to 90µL. A signal repeatability of<2% RSD of peak height was found. Analyte recovery evaluated by spiking of different natural water samples was well suited for routine analysis with sub-micromolar limits of detection.
- MeSH
- chemické látky znečišťující vodu analýza MeSH
- chromatografie metody MeSH
- formiáty chemie MeSH
- měď analýza MeSH
- minerální vody analýza MeSH
- pitná voda analýza MeSH
- pyridiny chemie MeSH
- resorcinoly chemie MeSH
- sírany chemie MeSH
- sladká voda analýza MeSH
- železo analýza MeSH
- zinek analýza MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
A new HPLC column-switching method using large volume sample injection and fused-core columns for on-line solid phase extraction have been developed for the determination of the following carbamates and pyrethroids: aldicarb, carbaryl, pirimicarb, carbofuran, kadethrin, flumethrin, fenpropathrin, fenoxycarb, tau-fluvalinate and fenvalerate, in surface water samples. Sudan I was used as internal standard. The proposed method was performed using 100 µl sample injection followed by an on-line solid phase extraction procedure and finally the compounds were identified and quantified by liquid chromatography with ultraviolet detection. The separation was carried out on C-18 reversed phase column based on fused-core particle technology. The influence of the injected sample volume, the variables affecting to SPE process and the conditions for the separation on an analytical column, were studied and optimized. The limits of detection ranged from 5.5 to 8.9 µg L(-1), and limits of quantification from 18.4 to 29.7 µg L(-1), while inter- and intra-day variability was under 15%. This new analytical procedure was satisfactorily applied for the determination of these organic pollutants in surface water samples located in Czech Republic. Concentration levels were found for some of these pollutants up to 26.11 µg L(-1) in the river Elbe and up to 34.53 µg L(-1) in the closed lakes samples.
- MeSH
- chemické látky znečišťující vodu analýza MeSH
- chromatografie kapalinová MeSH
- extrakce na pevné fázi metody MeSH
- insekticidy analýza MeSH
- jezera MeSH
- karbamáty analýza MeSH
- monitorování životního prostředí metody MeSH
- on-line systémy MeSH
- organické látky analýza MeSH
- pyrethriny analýza MeSH
- řeky MeSH
- reprodukovatelnost výsledků MeSH
- spektrofotometrie ultrafialová MeSH
- voda chemie MeSH
- vysokoúčinná kapalinová chromatografie metody MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Geografické názvy
- Česká republika MeSH
The present study describes an effect of reaction condition of pre-column derivatization of alkylphenols (APs): bisphenol A (BPA), 4-tert-octylphenol (4-t-OP), 4-octylphenol (4-OP), 4-n-nonylphenol (4-n-NP), and isomers of 4-nonylphenol (iso-NP) with 5-(dimethylamino) naphthalene-1-sulfonyl chloride (dansyl chloride, DNSC) on their LC-ESI-MS/MS determination in water samples. Chemical derivatization improves the sensitivity and selectivity of LC-MS/MS analysis. In principle, alkylphenols can be analyzed by LC-MS/MS without derivatization. However, pre-column derivatization of APs increases the sensitivity up to 1000 times in comparison with the analysis of underivatized alkylphenols. Reaction conditions affecting formation of the DNSC-derivatives, such as various solvent, reaction temperature, reaction time, DNSC concentration and pH values were tested. The most suitable conditions, in terms of achieving a high sensitivity, resulting from this study are: acetonitrile as reaction solvent, 60 min as reaction time, 60 °C as reaction temperature, pH values 10.5, 0.5 mg mL(-1) as DNSC concentration. Calibration curves are linear at least in the range of 1-1000 ng mL(-1), limits of detection (LOD) and limits of quantification (LOQ) ranging from 0.02 to 0.25 pg/injection and from 0.08 to 0.83 pg/injection, respectively. The improved procedure was successfully applied for the analysis of APs and BPA in real water samples. The median concentration of BPA and iso-NP obtained in bottled waters was 4.7 ng L(-1) and 33.5 ng L(-1), respectively. The median concentration of 4-t-OP was 1.3 ng L(-1.)
- MeSH
- benzhydrylové sloučeniny analýza MeSH
- chemické látky znečišťující vodu analýza MeSH
- chromatografie kapalinová metody MeSH
- fenoly analýza MeSH
- indikátory a reagencie MeSH
- limita detekce MeSH
- pitná voda analýza MeSH
- sloučeniny dansylu chemie MeSH
- tandemová hmotnostní spektrometrie metody MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
Concentrations and fluxes of total and methylmercury were determined in surface sediments and associated with settling particles at two sites in Lake Geneva to evaluate the sources and dynamics of this toxic contaminant. Total mercury concentrations measured in settling particles were different throughout the seasons and were greatly influenced by the Rhone River particulate inputs. Total mercury concentrations closer to shore (NG2) ranged between 0.073 ± 0.001 and 0.27 ± 0.01 μg/g, and between 0.038 ± 0.001 and 0.214 ± 0.008 μg/g at a site deeper in the lake (NG3). Total mercury fluxes ranged between 0.144 ± 0.002 and 3.0 ± 0.1 μg/m2/day at NG2, and between 0.102 ± 0.008 and 1.32 ± 0.08 μg/m2/day at NG3. Combined results of concentrations and fluxes showed that total mercury concentrations in settling particles are related to the season and particle inputs from the Rhone River. Despite an observed decrease in total mercury fluxes from the coastal zone towards the open lake, NG3 (~ 3 km from the shoreline) was still affected by the coastal boundary, as compared to distal sites at the center of the lake. Thus, sediment focusing is not efficient enough to redistribute contaminant inputs originating from the coastal zones, to the lake center. Methylmercury concentrations in settling particles largely exceeded the concentrations found in sediments, and their fluxes did not show significant differences with relation to the distance from shore. The methylmercury found associated with settling particles would be related to the lake's internal production rather than the effect of transport from sediment resuspension.
- MeSH
- chemické látky znečišťující vodu analýza MeSH
- geologické sedimenty analýza MeSH
- jezera analýza chemie MeSH
- methylortuťné sloučeniny analýza MeSH
- monitorování životního prostředí MeSH
- řeky MeSH
- roční období MeSH
- rtuť analýza MeSH
- Publikační typ
- časopisecké články MeSH
- Geografické názvy
- Švýcarsko MeSH
Part I on head-column field-amplified sample stacking comprised a detailed study of the electrokinetic injection of a weak base across a short water plug into a phosphate buffer at low pH. The water plug is converted into a low conductive acidic zone and cationic analytes become stacked at the interface between this and a newly formed phosphoric acid zone. The fundamentals of electrokinetic processes occurring thereafter were studied experimentally and with computer simulation and are presented as part II. The configuration analyzed represents a discontinuous buffer system. Computer simulation revealed that the phosphoric acid zone at the plug-buffer interface becomes converted into a migrating phosphate buffer plug which corresponds to the cationically migrating system zone of the phosphate buffer system. Its mobility is higher than that of the analytes such that they migrate behind the system zone in a phosphate buffer comparable to the applied background electrolyte. The temporal behaviour of the current and the conductivity across the water plug were monitored and found to reflect the changes in the low conductivity plug. Determination of the buffer flow in the capillary revealed increased pumping caused by the mismatch of electroosmosis within the low conductivity plug and the buffer. This effect becomes elevated with increasing water plug length. For plug lengths up to 1% of the total column length the flow quickly drops to the electroosmotic flow of the buffer and simulations with experimentally determined current and flow values predict negligible band dispersion and no loss of resolution for both low and large molecular mass components.
The fundamentals of electrokinetic injection of the weak base methadone across a short water plug into a phosphate buffer at low pH were studied experimentally and with computer simulation. The current during electrokinetic injection, the formation of the analyte zone, changes occurring within and around the water plug and mass transport of all compounds in the electric field were investigated. The impact of water plug length, plug injection velocity, and composition of sample, plug and background electrolyte are discussed. Experimental data revealed that properties of sample, water plug and stacking boundary are significantly and rapidly altered during electrokinetic injection. Simulation provided insight into these changes, including the nature of the migrating boundaries and the stacking of methadone at the interface to a newly formed phosphoric acid zone. The data confirm the role of the water plug to prevent contamination of the sample by components of the background electrolyte and suggest that mixing caused by electrohydrodynamic instabilities increases the water plug conductivity. The sample conductivity must be controlled by addition of an acid to prevent generation of reversed flow which removes the water plug and to create a buffering environment. Results revealed that a large increase in background electrolyte concentration is not accompanied with a significant increase in stacking.
