Comparison of solvent extraction and solid-phase extraction for the determination of organochlorine pesticide residues in water.

Solid-phase extraction (SPE) of organochlorine pesticide residues from environmental water samples was evaluated using octadecyl (C18)-bonded porous silica. The efficiency of SPE of these pesticide residues from reagent water samples at 1-5 micrograms dm-3 levels was compared with those obtained by solvent extraction with hexane and Freon TF (trichlorotrifluoroethane). Average recoveries exceeding 80% for these organochlorine pesticides were obtained via the SPE method using small cartridges containing 100 mg of 40 microns C18-bonded porous silica. The average recovery by solvent extraction with hexane and Freon TF exceeded 90% in both instances. It was concluded that the recoveries and precision for the SPE of organochlorine pesticides were poorer than those for the solvent extraction method. Organochlorine pesticide residue levels in environmental water samples from two major rivers flowing through predominantly rice-growing areas were monitored by gas chromatography using the solvent extraction method with hexane. Exceptionally high levels of organochlorine pesticide residues such as BHC, DDT, heptachlor, endosulfan and dieldrin were found in these water samples.     

Determination of triazines and organophosphorus pesticides in water samples using solid-phase extraction.

Octadecyl (C18)-bonded porous silica was evaluated for the extraction of triazine and organophosphorus pesticides from natural water. The extraction results showed an effective performance when 11 of water was passed through small glass columns containing 500 mg of 50-100-microns C18 bonded porous silica. The adsorbed compounds were removed with ethyl acetate, evaporated to 200 microliters and determined by gas chromatography. The overall average recoveries were greater than 85% except for dimethoate and trichlorfon. Application of this procedure to the analysis of natural water samples gave results that agree well with those obtained by solvent extraction methods.     

Rapid determination of chlorinated pesticides using CN-bonded cartridges followed by GC-ECD

Summary Gas chromatography of chlorinated pesticides in water is carried out after adsorption of a 50 mL sample using a cartridge containing 100 mg CN-bonded porous silica and extraction with 500 L pentane. The average recovery for eight organochloride pesticides at 1 ppb was >95%. The procedure described is simple, selective and reproducible.     

Trace analysis of triazines and organophosphorus pesticides in water

A method for the determination of trace levels of triazines and organophosphorus pesticides in water is presented. The extraction method is based on a solid-phase extraction on C-18 bound silica SPE cartridges. A precolumn filled with Merck C-18 bound silica and home-made C-18 bound silica have been tested at a flow-rate of 3 ml/min with comparable preconcentration yields. A SIM-MS method using a ¹⁵N labelled internal standard has been developed for the organophosphorus pesticides. Detection limits lower than 1 g/L have been obtained. Separations have been carried out on a conventional GC column OV 17 (1 m) and a capillary column OV 17 (25 m) with a temperature program from 150° C (2 min) to 300° C (rate of 6° C/min).     

Determination of N-pesticides in natural waters

Summary Using RP-C18 material in cartridges to preconcentrate natural water samples, a number of important GC-detectable nitrogen containing pesticides can be analysed. This should be a first step to a simple monitoring of these water constituents for which a routine survey proved to be obligate in the near future.

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Bestimmung von N-Pesticiden in natürlichen Wasserproben

     

Trace analysis of triazines and organophosphorus pesticides in water

A method for the determination of trace levels of triazines and organophosphorus pesticides in water is presented. The extraction method is based on a solid-phase extraction on C-18 bound silica SPE cartridges. A precolumn filled with Merck C-18 bound silica and home-made C-18 bound silica have been tested at a flow-rate of 3 ml/min with comparable preconcentration yields. A SIM-MS method using a (15)N labelled internal standard has been developed for the organophosphorus pesticides. Detection limits lower than 1 microg/L have been obtained. Separations have been carried out on a conventional GC column OV 17 (1 m) and a capillary column OV 17 (25 m) with a temperature program from 150 degrees C (2 min) to 300 degrees C (rate of 6 degrees C/min).     

Comparison of silica gel modified with three different functional groups with C-18 and styrene-divinylbenzene adsorbents for the analysis of selected volatile flavor compounds

A comparison of SPE cartridges produced in authors laboratory containing silica modified by addition of three functional moieties with standard C-18 and SDVB cartridges was made in terms of their applicability for the isolation of flavor compounds. Compounds found in wine and grapes were used for model mixture, which was spiked into a grape juice. Functionalized phases for SPE were prepared modifying silica gel with alkoxysilanes with different functional groups: (3-(phenylamino)-propyltrimethoxysilane, octyltriethoxysilane and octadecyl-silane. The functionalization was carried out by the dry method, which resulted 5, 10 and 20 weight parts of initial support. Functionalized phases were characterized using FT-IR, elemental analysis and NMR.Performance for new phases compared to “standard” ones (C-18 and SDVB (styrene–divinylbenzene) varied, depending on the group or type of analyzed compound. They were more efficient in extraction of methyl anthranilate and vanilins. For extraction of terpenes, C-6 alcohols, isoprenoids, benzene derivatives and phenols their efficiency was comparable to that of C-18.Functionalized laboratory-made mixed phases are suitable for extraction of flavor compounds from grape juice. They are suitable for extraction of compounds belonging to different chemical classes with the efficiency comparable to C-18 and SDVB phases. The production of such functionalized phases can be easily performed in the laboratory, at a very low cost, comparing to C-18 or SDVB cartridges. This makes the proposed functionalized phases an interesting alternative, in sample preparation for analysis and particularly in preparative/flash chromatography.     

Multiresidue analysis of polar pesticides in surface and drinking water by on-line enrichment and thermospray LC-MS

In the search for a fast and robust sample handling and preparation step to analyse various pesticides at trace levels in aqueous samples, an on-line trace enrichment has been combined with our thermospray LC-MS method [1] allowing both selective identification and a quantification down to the lower ng/L level. 51 polar pesticides were investigated by applying solid phase extraction to 50–100 ml aqueous samples using small cartridges filled with 40 mg adsorbent. Prior to their liquid chromatographic separation, the enriched analytes were eluted from the solid phase with the initial methanol/water gradient composition of the HPLC onto the analytical column using column switching techniques. A base-deactivated C₁₈ material and the two styrene-divinylbenzene copolymers PLRP-S and PRP-1 were tested for enrichment in combination with a C₈-bonded silica analytical column. The method developed was evaluated with respect to recoveries, precision, limits of detection and linearity. Furthermore, it was applied to various environmental samples. Apart from a few compounds of higher polarity, most of the pesticides show recoveries >60% (often >80%) with relative standard deviations between 1–15%. Overall method detection limits are in the range of 1–100 ng/L allowing, with one exception, a ready verification of the pesticide limit of 100 ng/L set in the EU drinking water guideline [2].     

Cyanopropyl Bonded-Phase Cartridges for Trace Enrichment of Dioxins and Chlorinated Pesticides from Water Samples

Gas chromatography of dioxins and chlorinated pesticides in water samples has been performed after adsorption from 50 to 100 mL sample on to a cartridge containing 100 mg cyanopropyl-bonded porous silica. The dioxins and chlorinated pesticides were desorbed with 2 mL carbon disulfide, which is concentrated and analysed by gas chromatography coupled with an electron-capture detector. The average recovery of 0.20 ng mL^?1 of each chlorinated pesticide and of 0.50 ng mL^?1 of each dioxin from distilled water and river water samples (50 mL) is ≥97.2% with a standard deviation (SD) ≤ 2.6. In the dioxin separation from chlorinated pesticides the recovery of dioxins at levels of 0.1–0.5 ng mL^?1 is ≥97.9% with a SD ≤ 1.3, with traces of aldrin, heptachlorepoxide and 4,4′-DDD (≤1.7%) by the CN-Sep-Pak cartridge, while the recovery of chlorinated pesticides at levels of 0.05–0.2 ng mL^?1 is ≥97.4% with a SD ≤ 1.5, with traces of hep-dioxin (2.4%) and penta-dioxin (1.0%) by the C₁₈-Sep-Pak cartridge connected “in series” to the CN-Sep-Pak cartridge.     

Coverage homogenity of chemically bonded C18 phases for HPLC. Investigation of the changes in the free surface energy of the packings

Summary Packings containing chemically bonded C₁₈ groups with different coverage density were prepared using monochlorooctadecylsilane. The method permitting the determination of the free surface energy on the basis of adsorption measurements of two different liquids, noctane and water, was utilized to evaluate the coverage homogeneity of the silica gel surface by the alkylsilyl ligands. It was found that the packing is characterized by a coverage greater than 3.8 mol/m², it is homogenous and the support surface is fully screened.     

Solid-Phase Extraction,Clean-pp and Liquid Chromatography for Routine Multiresidue Analysis of Neutral and Acidic pesticides In Natural Waters in One Run

Abstract

Solid-phase extraction using C₁₈ silica cartridges, liquid chromatography analysis and UV diode array detection were investigated for the routine trace-level determination of neutral pesticides over a wide range of polarity. Detection limits below the 0.1 μg/1 range were easily obtained in drinking water. If neutral and acidic pesticides over a wide range of polarity have to be determined in the same run, samples have to be acidified to obtain good recoveries of extraction. The effect of the sample matrix was studied and detection limits in the 0.1 μg/1 range were obtained in drinking water except for the more polar ones which are in the interfering peak of humic and fulvic acids. For surface water, a clean-up step using a Florisil cartridge has to be included in the procedure that allows detection limits in the range 0.05–0.3 μg/1.     

Automated Extraction of Drugs from Biological Fluids

Abstract

An automated continuous flow liquid-liquid extraction procedure is described for the separation of the H₂-antagonist loxtidine from plasma samples containing two metabolites which interfere in the radioimmunoassay of the drug. The extraction of the bronchodilator salbutamol was studied using the DuPont Prep I automated liquid solid extraction apparatus, with a 12 cartridge capacity, and a vacuum extraction box designed in this laboratory to hold 30 Sep-pak C-18 (Waters Associates) cartridges. Twenty-four plasma samples per hour can be automatically processed with the Prep I. Although the vacuum box is not fully automated 45 plasma samples per hour can be processed. The Prep I can only be used with DuPont XAD, strong cation and anion exchange cartridges. Cartridges containing alumina, silica, floril, cation and anion exchange resins and reverse phase packings can all be used with the vacuum extraction box. The latter costs only a fraction of the Prep I and therefore each analyst can have his own unit.     

Separation of polychlorinated biphenyls from chlorinated pesticides using aminopropyl bonded-phase cartridge and determination by GC-ECD

Summary Gas chromatography of polychlorinated biphenyls and chlorinated pesticides in water samples is carried out after adsorption from a 25–500 mL sample, on a cartridge containing 100 mg aminopropyl-bonded porous silica. The clean-up step in which the PCBs and chlorinated pesticides are separated in different eluates is achieved by passing 25 mL of 40% aqueous methanol through the NH₂ Sep-Pak cartridge. The PCBs are desorbed with 500 μL ethylacetate, which is concentrated and analysis by GC-ECD. The average recovery, at 1 ppb is >97% with a standard deviation <2. The limits of detection are 0.1 ng μL⁻¹ and 5 pg μL⁻¹ respectively for Cl₃-PCB and Cl₈-PCB congeners. In the separation of PCBs from the chlorinated pesticides tested in this work, only the Aldrin is adsorbed for 60% with the PCBs by the NH₂ Sep-Pak cartridge. The method described is rapid, simple and reproducible.     

Diol sep-pak cartridges for enrichment of polychlorobiphenyls and chlorinated pesticides from water samples; determination by GC-ECD

Summary Gas chromatography of polychlorinated biphenyls and chlorinated pesticides in water samples has been performed after adsorption from a 20–200-mL sample on to a cartridge containing 100 mg diol-bonded porous silica. The PCBs are desorbed with 500 μL ethyl acetate, which is concentrated and analysed by gas chromatography with electron-capture detection (GC-ECD). The average recovery of 0.1 ng mL⁻¹ PCB congeners from distilled water and from Aniene river water is≥95% (standard deviation≤2.8). Average recoveries of 25 ng mL⁻¹ Aroclor 1254 from distilled water and from Aniene river water were, respectively, 94.4% and 92.5% (standard deviation 5.8). In the separation of PCB congeners from the chlorinated pesticides only the aldrin (40%) was eluted with the PCBs from the diol Sep-Pak cartridge by aqueous methanol. The method described is simple and reproducible.     

The influence of mercury(II) on the extraction efficiency of herbicides from water

In this work, the effect of Hg(II) on the extraction efficiency of triazine and phenylurea herbicides from water samples was tested. The results showed that in the presence of Hg(II), the recoveries of the s-triazine herbicides (except hexazinon) from styrene divinylbenzene (SDVB) cartridges were significantly reduced using acetonitrile as the elution solvent, whereas acidified methanol quantitatively eluted all the herbicides. Consequently, the loss in the recoveries was not due to degradation of the compounds but rather due to irreversible adsorption onto the resin. The adsorption is probably due to ternary complex formation between the compounds, Hg(II) and the polymeric resin. The chemical structure and the basicity of the compounds affected their interaction with Hg(II). When using octadecyl (C18) cartridges, only atraton was affected. Mercury did not affect the liquid–liquid extraction of the herbicides. The findings suggest that acidic methanol is a suitable elution solvent of s-triazines from mercury-loaded water samples.     

Neutron activation analysis in forensic investigations: Trace elements characterization of cigarettes

A new type of silica-based chelating extraction resin, DtBuCH18C6/SiO₂-P, was prepared by impregnating a crown ether derivative, 4,4￠,(5￠)-di(tert-butylcyclohexano)-18-crown-6 (DtBuCH18C6), into the porous silica/polymer composite particles (SiO₂-P). The adsorption of Sr(II) and some other fission product elements was investigated by a batch adsorption experiment in HNO₃ This revised version was published online in July 2006 with corrections to the Cover Date.     

Kinetics of the adsorption of strontium(II) by a novel silica-based 4,4'',(5'')-di(tert-butylcyclohexano)-18-crown-6 extraction resin in nitric acid medium

A new type of silica-based chelating extraction resin, DtBuCH18C6/SiO₂-P, was prepared by impregnating a crown ether derivative, 4,4,(5)-di(tert-butylcyclohexano)-18-crown-6 (DtBuCH18C6), into the porous silica/polymer composite particles (SiO₂-P). The adsorption of Sr(II) and some other fission product elements was investigated by a batch adsorption experiment in HNO₃ medium. It was found that Sr(II) exhibits a strong adsorption onto the extraction resin, while the other fission product elements show almost no or only weak adsorption. The adsorption kinetics of Sr(II) was explained by assuming as the rate-controlling step the complex-formation reaction between Sr(II) and DtBuCH18C6 contained in the extraction resin. The rate equation of Sr(II) adsorption was determined as:-d[Sr(II)]/dt = k[Sr(II)][DtBuCH18C6][NO₃ ^–]^0.5.     

Adsorption of CsOH on controlled porous glasses

Adsorption of CsOH has been studied for 18 samples of porous glasses prepared from different raw glass materials by means of different thermal and chemical treatment. For all the samples studied and for 3 samples of chromatographic silica gels the adsorption capacity in relation to CsOH is proportional to the BET surface area and equals 4 mol of cesium per 1 m² of BET surface.     

Simultaneous determination of selected endocrine disrupters (pesticides,phenols and phthalates) in water by in-field solid-phase extraction (SPE) using the prototype PROFEXS followed by on-line SPE (PROSPEKT) and analysis by liquid chromatography-atmospheric pressure chemical ionisation-mass spectrometry

In this study, a new procedure, based on on-line solid-phase extraction (SPE) and analysis by liquid-chromatography-atmospheric pressure chemical ionization-mass spectrometry (LC-APCI-MS), has been developed for the simultaneous, multianalyte determination of 21 selected pesticides, phenols and phthalates in water. SPE was carried out on polymeric PLRP-s cartridges by percolating 20 mL-samples. For sample preconcentration, the performance of a prototype programmable field extraction system (PROFEXS) was evaluated against the commercial laboratory bench Prospekt system used for method development. The Profexs is designed for the automated on-site sampling, SPE preconcentration, and storage of up to 16 samples in SPE cartridges. These cartridges are further eluted and on-line analyzed with the Prospekt coupled to the chromatographic system. In the optimized method, where completely on-line SPE-LC-MS analysis of the samples is carried out with the Prospekt in the laboratory, detection limits lower than 100 ng/L, and satisfactory precision (relative standard deviations <25%) and accuracies (recovery percentages >75%) were obtained for most investigated compounds from the analysis of spiked Milli-Q water. The extraction efficiency achieved with the Profexs was comparable to that of the Prospekt for most compounds and somewhat lower for the most apolar analytes, probably due to adsorption on the pump filters. The completely on-line optimized method was applied to the analysis of surface water, ground water and drinking water from a waterworks in Barcelona. Some pesticides and phenols were found in both surface water and groundwater at ng/L or µg/L levels, but not in the final drinking water. Di(2-ethylhexyl)phthalate (DEHP) was present in all samples investigated, including blanks. To the author's knowledge, this is the first work describing the application of a fully automated on-line SPE-LC-MS method for the simultaneous analysis of pesticides, phenols, and phthalates in water, and the second one that examines the possibilities of the prototype Profexs for automated on-site SPE preconcentration of organic pollutants from water samples.     

Comparison of different solid phase extraction materials and techniques by application of multiresidue methods for the determination of pesticides in water by high-performance liquid chromatography (HPLC)

Solid phase extraction materials and techniques (C-18 EMPORE^® disks, polystyrenedivinylbenzene (SDB) EMPORE^® disks, C-18 BondElut cartridges and ENVI-Carb cartridges) are compared for the preconcentration of 33 basic/neutral and 10 acidic/phenolic pesticides and three metabolites in water. The efficiency of the different extraction procedures was investigated by application of appropriate multiresidue separation methods by reversed phase-high performance liquid chromatography with UV-diode-array detection. Calibrations were performed with multicomponent standard mixtures and recoveries, relative standard deviations and determination limits were calculated for comparing the described enrichment methods. Experiences made in practical application of the different techniques and materials were also considered for the final evaluation.