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D Barceló

Publications and source records attributed to D Barceló.

At least 37 records · Page 2Linked to original sources

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 microg/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.

Atmospheric Pressure↗

Endocrine disrupting compounds and other emerging contaminants in the environment: a survey on new monitoring strategies and occurrence data.

An overview of Toxicity Identification and Evaluation (TIE) procedures, used for the effect-based analysis of endocrine disrupting compounds (EDCs) in environmental samples, is presented. Future trends in advanced chemical analysis of EDCs and some emerging contaminants are outlined. The review also gives an overview of concentration levels found in environmental samples and discusses the correlation of calculated estrogenicity (based on chemical analysis of target EDCs) with that measured by various bioassays.

Animals↗

Comparison of gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry for the determination of fatty and resin acids in paper mill process waters.

A comparative study of the performance of liquid chromatography (LC)-atmospheric pressure chemical ionisation (APCI)-mass spectrometry (MS) and gas chromatography (GC)-mass spectrometry techniques for the determination of resin and fatty acids from paper mill process waters was carried out. These compounds are responsible for the high toxicity of paper mill effluents and little research has been carried out regarding their analysis using mass spectrometric techniques. To prove the usability of GC and LC-MS, 16 treated and untreated water samples of recycle, kraft and pulp paper mills were analysed and good agreement was observed as regards to compounds detected and corresponding concentrations. This paper also reports the limits of detection, recoveries, reproducibility, linearity and precision using the two methods. GC-MS presented better selectivity and lower detection limits (below 0.2 microg/l), but derivatization of the extracts and the short life of derivatives (12-24 h) made the technique tedious and prone to high variations. Although LC-APCI-MS presented coelution of the non-aromatic resin acids, it also showed good sensitivity (limits of detection <3 microg/l) and permitted the detection of resin and fatty acids at microg/l level. In addition, since samples could be directly injected to the chromatographic system, LC-APCI-MS was proven as a powerful technique for quick and unequivocal quality control during papermaking.

Atmospheric Pressure↗

Direct determination of resin and fatty acids in process waters of paper industries by liquid chromatography/mass spectrometry.

Liquid chromatography/mass spectrometry (LC/MS)-based methods were developed for the analysis of 10 resin acids and five fatty acids in process waters of paper industries. No fragmentation of target compounds was observed using atmospheric pressure chemical ionization (APCI) with negative ionization. The [M - H](-) ion permitted the individual quantification of fatty and aromatic resin acids, whereas the non-aromatic resin acids presented a single and common ion at m/z 301. Separation with two columns of different polarity permitted peak confirmation. The method that used a C(8) column with 2-propanol in the mobile phase allowed a certain separation and identification of the non-aromatic resin acids, whereas the method using a C(18) column provided detection limits 10-fold lower for fatty acids. Limits of detection were 0.10 ng for all compounds. Direct sample introduction was compared with liquid-liquid extraction, with similar recoveries (70-101%). Whereas slightly lower detection limits were obtained with liquid-liquid extraction, better reproducibility was observed for direct sample introduction. Resin and fatty acids were determined in process waters of several paper industries. Palmitic, dehydroabietic and non-aromatic resin acids were encountered in most water samples, at levels between 22 and 403 micro g l(-1). LC/MS with direct sample introduction was found to be a good alternative to traditional liquid-liquid extraction and gas chromatography for the analysis of such compounds since no derivatization was required and sample manipulation was minimal.

Calibration↗

Low nanogram per liter determination of halogenated nonylphenols, nonylphenol carboxylates, and their non-halogenated precursors in water and sludge by liquid chromatography electrospray tandem mass spectrometry.

A new LC-MS-MS method for quantitative analysis of nonylphenol (NP), nonylphenol carboxylates (NPECs), and their halogenated derivatives: brominated and chlorinated nonylphenols (BrNP, ClNP), brominated and chlorinated nonylphenol carboxylates (BrNPE(1)C and ClNPE(1)C) and ethoxycarboxylates (BrNPE(2)C and ClNPE(2)C) in water and sludge has been developed. Electrospray negative ionization MS-MS was applied for the identification of above mentioned compounds. Upon collision-induced dissociation, their deprotonated molecules gave different fragments formed by the cleavage of the alkyl moiety and/or (ethoxy)carboxylic moiety. For halogenated compounds a highly diagnostic characteristic pattern of isotopic doublet signals was obtained and fragmentation yielded, in addition to above mentioned ions, [Br](-) and [Cl](-), respectively. Quantitative analysis was done in the multiple reaction monitoring (MRM) mode, using two specific combinations of a precursor-product ion transitions for each compound. Additionally, for halogenated compounds two specific channels for each transition reaction, corresponding to two isotopes, were monitored and the ratio of their abundances used as an identification criterion. The method has been validated in terms of sensitivity, selectivity, accuracy, and precision and was applied to the analysis of water and sludge samples from drinking water treatment plant (DWTP) of Barcelona (Catalonia, NE Spain). Halogenated NP and NPECs were detected in prechlorinated water in concentrations up to 315 ng/L, BrNPE(2)C being the most abundant compound. In the DWTP effluent non-halogenated compounds were detected at trace levels (85, 12 and 10 ng/L for NP, NPE(1)C, and NPE(2)C, respectively), whereas concentration of halogenated derivatives never exceeded 10 ng/L. Nonylphenol, brominated and chlorinated NPs were found in flocculation sludge in concentrations of 150, 105, and 145 microg/kg, respectively. Acidic polar metabolites were found in lower concentrations up to 20 microg/kg.

Carboxylic Acids↗

Feminization of wild carp, Cyprinus carpio, in a polluted environment: plasma steroid hormones, gonadal morphology and xenobiotic metabolizing system.

Wild carp, Cyprinus carpio, were sampled in January and March 2000 in a section of the Anoia River (NE Spain) known to be polluted by estrogenic compounds. At each sampling time, three groups were distinguished: (1) apparently normal males; (2) apparently normal females; and (3) affected fish. The latter were characterized by the simultaneous development of male and female tissue in their gonads at a macroscopical level (six out of 31 fish sampled at this particular point), or testicular atrophy (three out of 31). Plasmatic and hepatic vitellogenin (VTG) levels and plasma testosterone (T) and estradiol (E2) were measured to observe the particular estrogenic response of the affected fish. Moreover, the response in the xenobiotic metabolizing capacity in liver was tested. This involved the analysis of mixed function oxygenase (MFO) system such as: total cytochrome P450 content, NAD(P)H cytochrome c reductases and the associated CYP1A1, EROD activity. Also, glutathione S-transferase (GST) and UDP-glucuronosyltransferase (UDPGT) as detoxifying enzymes were measured. Our results showed: (1) a highly variable VTG content in all fish groups; (2) an increase in sex hormones content in March for the female group; and (3) an enhanced xenobiotics metabolism in the affected fish group, measured as total cytochrome P450, EROD activity in the January survey and cytosolic GST in March. The observed increase in VTG, sex hormones and in most of the enzymatic activities from January to March that could also be attributed to higher water temperature.

Animals↗

Analysis and toxicity of methomyl and ametryn after biodegradation.

The controlled biodegradation of ametryn and methomyl has been performed, in accordance with the OECD Zahn-Wellens/EMPA procedure, by use of an enriched mixture of activated sludge collected from three domestic waste-water-treatment plants (WWTP). During the process concentrations of ametryn and methomyl in the water samples were isolated by solid-phase extraction (SPE); recovery rates were 98.9 and 93.2 for methomyl and ametryn, respectively. Liquid chromatography-mass spectrometry (LC-MS) was used to determine final pesticide concentrations and for metabolite identification. The efficiency of aerobic biodegradation of ametryn and methomyl was evaluated by measuring both the decrease in the concentration of the pesticides and global properties such as the chemical oxygen demand (COD). The acute toxicity of ametryn and methomyl was evaluated by use of the ToxAlert100 biological test, which is based on inhibition of the bioluminescence of Vibrio fischeri. There was significant correlation between results from primary and ultimate biodegradation and those from determination of toxicity. Pesticide concentrations were always reduced to below the limit of detection in less than 17 days. High COD removal (90-96%) was achieved in 28 and 18 days for methomyl and ametryn, respectively.

Biodegradation, Environmental↗

Determination of toxic compounds in paper-recycling process waters by gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry.

Three analytical methods were developed for the determination of toxic compounds in recirculating waters of a paper-recycling industry. Three main groups of compounds were considered: (i) wood extractives originated from the raw material; (ii) biocides added during the production process and (iii) surfactants and other adjuvants present in the formulates of these biocides. Wood extractives considered in this study included fatty and resin acids. They were analysed by liquid-liquid extraction using methyl tert.-butyl ether, followed by gas chromatography-mass spectrometry for previous formation of the respective trimethylsilyl esters. Water samples were also extracted with Oasis HLB (copolymer [poly(divinylbenzene-co-N-vinylpyrrolidone]) solid-phase extraction cartridges of 60 mg and analysed by liquid chromatography-electrospray mass spectrometry for the determination of additives and biocides. Using these two approaches levels up to 15 mg/l for total resin and fatty acids, 5 mg/l for alkylbenzene sulfonates and 2-(thiocyanomethylthio)benzotiazol, 100 microg/l for bisphenol A and 2,2-dibromo-3-nitrilepropionamide, and 300 microg/l for nonylphenol ethoxycarboxylate were detected in process waters at different production treatment stages. These levels are of relevance since poor water quality affects the paper-recycling process, the primary water treatment process and eventually, the environmental water quality.

Chromatography, Liquid↗

Pesticide toxicity assessment using an electrochemical biosensor with Pseudomonas putida and a bioluminescence inhibition assay with Vibrio fischeri.

Two different toxicity tests, an electrochemical biosensor Cellsense and a bioluminescence inhibition assay ToxAlert were performed in order to establish and compare the acute toxicity responses of different types of raw and spiked water for a selected group of pesticides. The selected compounds were endosulfan, chlorfenvinphos, dimethoate, fenamiphos, ametryn, deltamethrin and alpha-cypermethrin; all of them are used in large quantities for agricultural purposes. In the first step, the study of the toxicity responses for each individual pesticide with Milli-Q water was carried out. Next, the toxic responses of different mixtures of these pesticides in different water matrices, i.e., Milli-Q water, surface water, groundwater and wastewater were studied in order to evaluate (i) device advantages and limitations for the toxicity evaluation of real environmental samples, (ii) antagonistic or synergistic effects and (iii) the influence of the water matrices. The survey of pesticides in real samples was carried out using a combined method involving both chemical analysis and toxicity bioassays. Chemical analysis involved the use of solid-phase micro-extraction (SPME) followed by gas chromatography with electron capture detection (GC/ECD) or thermoionic specific detection (GC/TSD) with mass spectrometric confirmation (GC/MS).

Biosensing Techniques↗

Monitoring of the gasoline oxygenate MTBE and BTEX compounds in groundwater in Catalonia (northeast Spain).

Headspace (HS) gas chromatography with flame ionisation detection (HS-GC-FID) and purge and trap (P) gas chromatography-mass spectrometry (P) were used for the determination of methyl-tert-butyl ether (MTBE) and benzene, toluene, and xylenes (BTEX) in groundwater. In this work, we present the first data on the levels of MTBE and BTEX in different groundwater wells in the area of Catalonia (northeast Spain). This monitoring campaign corresponded to 28 groundwater wells that were located near petrol service stations, oil refinery storage tanks, and/or chemical industry at different locations of Catalonia during the period of 1998/1999. The levels of MTBE detected varied between 4-300 microg/l, but two sites had MTBE levels up to 3 and 13 mg/l. In many cases, the BTEX levels were below 1 microg/l, whereas 7 sites had levels varying from 19 microg/l up to 3 mg/l. Most of them were related to leakage from underground tanks in petrol service stations, while the remaining three corresponded respectively to chemical industrial pollution of undetermined origin and to a leak from high-ground petrol tanks in petrochemical refinery factories. The aquifers involved were constituted by detritus coarse materials, sands, and conglomerates. Piezometric levels were roughly comprised between 3 and 40 m, and permeability (K) and transmissivity (T) values were estimated from field measurements. The MTBE/BTEX ratio was also calculated and reached values up to 250. These values were expected, since if we consider that spilled oxygenated gasoline is the source of well contamination and based on solubility considerations alone, the MTBE source concentrations would be about 200 times higher than any BTEX compounds.

Benzene↗

Fate of MTBE and DCPD compounds relative to BTEX in gasoline-contaminated aquifers.

The aim of this communication is to provide preliminary results on MTBE monitoring, and at the same time to propose some new tracers of gasoline pollution in groundwater. An overview is presented on benzene-toluene-ethylbenzene-xylene (BTEX), methyl tertiary-butyl ether (MTBE), and dicyclopentadienes (DCPD) contents in gasoline formulations. Their specific fate in gasoline-contaminated aquifers are consistent with their physical-chemical properties.

Benzene↗

Optimization of congener-specific analysis of 40 polybrominated diphenyl ethers by gas chromatography/mass spectrometry.

The analysis by gas chromatography coupled with mass spectrometry (GC/MS) of 40 different congeners of polybrominated diphenyl ethers (PBDEs) containing 1-7 bromine atoms is described. Two different MS approaches were used, negative chemical ionization (NCI-MS) and electron ionization (EI-MS). Operating parameters such as electron energy and source temperature were optimized in order to obtain the maximum sensitivity in the EI-MS study. For NCI-MS analyses, the effects of the moderating gas (methane or ammonia), source temperature and system pressure were studied. The quality parameters of the two approaches tested were compared. NCI-MS gave detection limits between 30 fg and 1.72 pg, whereas EI-MS gave detection limits between 0.53 and 32.09 pg. The main advantage of EI-MS is that it provides better structural information. Moreover, the use of EI-MS allowed the use of an isotope dilution method for quantification, making the analysis more reliable at trace levels.

Environmental Pollutants↗

Congener-specific determination of dioxins and related compounds by gas chromatography coupled to LRMS, HRMS, MS/MS and TOFMS.

Their characteristics as persistent organic pollutant and their toxicity (2,3,7,8-TCDD is named as a known human carcinogen) make the dioxins and related compounds a focus of interest in environmental analytical chemistry. In view of the widespread distribution of dioxins in the environment, these compounds must be monitored in several matrices, such as air, effluents, soil, sludge and biological samples. The analytical methodologies are especially difficult owing to the complexity of the mixtures of congeners (210 PCDD/Fs and 209 PCBs) and to the low detection limits required (ppb to ppq). Moreover, time-consuming sample preparation steps are needed owing to the presence of a large number of interfering compounds. The different toxicity of each congener requires the development of congener specific methods. This review of trace dioxin determination by mass spectrometry (MS) includes sample preparation and chromatographic separation. In this Special Feature, the use of different MS techniques such as low-resolution MS (LRMS) and high-resolution MS (HRMS) is discussed in terms of selectivity and sensitivity. The performances of other MS techniques, such as tandem MS (MS/MS) and time-of-flight MS (ToFMS), are compared. Quantification techniques, especially the isotopic dilution method, are also discussed. Conclusions and future perspectives are outlined.

Carcinogens↗

Stability study and determination of benzene- and naphthalenesulfonates following an on-line solid-phase extraction method using the new programmable field extraction system.

Seven benzene- and naphthalenesulfonates (3-nitrobenzenesulfonate, 4-methylbenzenesulfonate, 1-hydroxy-4-naphthalenesulfonate, 1-amino-7-naphthalenesulfonate, 4-chlorobenzenesulfonate, 1-naphthalenesulfonate and 2-naphthalenesulfonate) were studied. A rapid method for quantifying aromatic sulfonated compounds from waste water samples was developed. This method consists in on-line in-field sampling and monitoring based on ion-pair solid-phase extraction with PLRP-S sorbent, using the new programmable field extraction system and ion-pair liquid chromatography with UV diode-array and electrospray mass spectrometry. Limits of detection for the studied compounds, using the SIM acquisition mode, ranged from 0.01 to 0.33 ng ml(-1). The influence of the aqueous matrix on the on-line SPE was checked by spiking ground and waste waters. Recoveries varied from 70 to 99% when 10 ml of water sample were enriched. The method was applied to the analysis of some environmental sewage samples. This study confirmed that high concentration levels of aromatic sulfonated compounds can be found in sewage samples. In addition, the stability of the seven studied sulfonated benzene and naphthalene compounds was investigated using on-line polymeric SPE pre-columns, based on the styrene-divinylbenzene polymer PLRP-S. Different storage conditions were tested to carry out the stability survey, which included storage at room temperature, at 4 degrees C and at -20 degrees C, during a period of up to 2 weeks. This study showed that the stability of aromatic sulfonic acids on disposable on-line SPE polymeric pre-columns is related to temperature and that the target compounds are more stable at lower temperatures.

Benzenesulfonates↗

Simultaneous determination of halogenated derivatives of alkylphenol ethoxylates and their metabolites in sludges, river sediments, and surface, drinking, and wastewaters by liquid chromatography-mass spectrometry.

A quantitative solid-phase extraction-liquid chromatography/mass spectrometry (SPE-LC/MS) method is described for the simultaneous analysis of halogenated byproducts of alkylphenolic compounds and their degradation products formed during chlorine disinfection in the presence of bromide ions. Compounds analyzed include brominated and chlorinated nonylphenol ethoxylates (XN-PEOs); octylphenol ethoxylates (XOPEOs); nonylphenols (XNP); nonylphenoxycarboxylates (XNPECs) and their precursors nonionic surfactants, alkylphenol ethoxylates (APEOs); and their metabolites formed during sewage treatment, alkylphenoxycarboxylates (APECs) and alkylphenols (APs). Target compounds were concentrated from water samples using a C18 SPE procedure. Extracts were analyzed using reversed phase LC/MS. The performances of both atmospheric pressure chemical ionization (APCI) and electrospray (ESI) interfaces were compared. ESI offered better sensitivity and specificity for a higher range of oligomers. Detection limits (LODs) for water samples were from 20 to 100 ng/L; and for sediment samples, from 2 to 10 microg/kg. Slightly higher LODs were obtained for sludge samples (5-25 microg/kg). Halogenated byproducts were found in sludge from Barcelona drinking water treatment plant in concentrations of 220 microg/kg for BrNP, 430 microg/kg for BrNPEOs (nEO = 1 - 2), and 1600 microg/kg for BrNPEOs (nEO = 3 - 15). The concentration of ClNPEOs was estimated to be in the order of 660 microg/kg (assuming the same response as BrNPEOs). Halogenated OPEOs were also identified, and their concentration was approximately 50 times lower than the concentration of NPEOs analogues. To our knowledge, this is the first method described that allows simultaneous determination of alkyphenol ethoxylates and halogenated derivatives, including degradation products.

Chromatography, High Pressure Liquid↗

Determination of haloacetic acids in aqueous environments by solid-phase extraction followed by ion-pair liquid chromatography-electrospray ionization mass spectrometric detection.

Haloacetic acids (HAAs) were determined in different water samples by a new, fast and simple analysis method based on enrichment of 50-ml water samples at pH 1.8 by solid-phase extraction (SPE) followed by liquid chromatography (LC) separation and electrospray ionization mass spectrometric detection in the negative ionization mode. Deprotonated (M-H)-haloacetates and decarboxylated (M-COOH)- ions were detected. Different polymeric SPE sorbents were tested, and LiChrolut EN was found to be the best material for the extraction. Complete LC separation of all compounds could only be achieved by ion-pair chromatography using triethylamine as volatile ion-pairing reagent. The detection limits were in the low microg/l range. High microg/l concentration levels for the chlorinated and brominated haloacetates were found in drinking water from a drinking water treatment plant in Barcelona, and the corresponding tap water. In swimming pool water samples from Catalonia mg/l levels and in surface river water from Portugal microg/l values were detected. These results confirm other recent reports on the ubiquitous occurrence of HAAs in aqueous environments.

Acetates↗

Determination of drugs in surface water and wastewater samples by liquid chromatography-mass spectrometry: methods and preliminary results including toxicity studies with Vibrio fischeri.

In the present work a combined analytical method involving toxicity and liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) was developed for the determination of pharmaceutical compounds in water samples. The drugs investigated were the analgesics: ibuprofen, ketoprofen, naproxen, and diclofenac, the decomposition product of the acetyl salicylic acid: salicylic acid and one lipid lowering agent, gemfibrozil. The selected compounds are acidic substances, very polar and all of them are analgesic compounds that can be purchased without medical prescription. The developed protocol consisted, first of all, on the use Microtox and ToxAlert 100 toxicity tests with Vibriofischeri for the different pharmaceutical drugs. The 50% effective concentration (EC50) values and the toxicity units (TU) were determined for every compound using both systems. Sample enrichment of water samples was achieved by solid-phase extraction procedure (SPE), using the Merck LiChrolut EN cartridges followed by LC-ESI-MS. Average recoveries loading 11 of samples with pH=2 varied from 69 to 91% and the detection limits in the range of 15-56 ng/l. The developed method was applied to real samples from wastewater and surface-river waters of Catalonia (north-east of Spain). One batch of samples was analyzed in parallel also by High Resolution Gas Chromatography coupled with Mass Spectrometry (HRGC-MS) and the results have been compared with the LC-ESI-MS method developed in this work.

Chromatography, Liquid↗

Use of solid-phase extraction in various of its modalities for sample preparation in the determination of estrogens and progestogens in sediment and water.

The environmental analysis of estrogens and progestogens at physiologically active concentrations (low ng/l range) requires the use of very sensitive and selective methods, which, in most cases, make necessary an extraction/purification step. In this study, various procedures for the determination of several estrogens (estriol, estradiol, ethynyl estradiol, estrone, and diethylstilbestrol) and progestogens (progesterone, norethindrone, and levonorgestrel) in environmental matrices, including water and river sediment, are described. In all procedures, final analysis of the target compounds is performed by reversed-phase liquid chromatography-diode array detection-mass spectrometry, whereas sample preparation always includes a solid-phase extraction (SPE) step. For this SPE step. various types of sorbents, protocols, and devices have been used, and their respective advantages and disadvantages are discussed. For the off-line SPE of estrogens and progestogens from water samples, a syringe type cartridge LiChrolut RP-18 (500 mg) was selected out of two other sorbents--LiChrolut EN (200 mg) and Isolut ENV (500 mg)--for use with the automated sample preparation instrument ASPEC XL. For the on-line SPE and analysis of water samples the 10 mm x 2 mm I.D. HySphere-Resin-GP cartridge, was preferred to the C18 Baker, the PLRP-S, and the Oasis HLB. for use with the Prospekt system. A completely manual protocol based on the use of Sep-Pak C18 Plus cartridges was developed for purification of sediment extracts. All procedures were shown to be linear over a wide range of concentration, exhibited satisfactory repeatability and accuracy, and reached limits of detection usually in the low ng/l and ng/g range. Comparatively, the on-line method was shown to be advantageous in terms of automation and general method performance.

Chromatography, Liquid↗