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The weathering of natural and artificial stones in the baroque church of S. Pietro in Valle (Fano-Italy).

The church of San Pietro in Valle in Fano is with good reason considered one of the outstanding examples of baroque art in Central Italy. Currently the church is in a serious degradation status. For this reason, and in order to devise a correct conservative restoration project, a scientific study has been carried out, aimed at characterizing mortars used for the application of marble decorations and the different degradation products occurring in the church (i.e. pulverizations, encrustations, salt efflorescences, and condensation water). In the following, results obtained analyzing the different sample typologies by optical microscopy, X-ray diffraction, electron scanning microscopy with energy-dispersion micro-analytical system, ion chromatography, and head-space solid phase microextraction-gas chromatography-mass spectrometry will be reported.

Architecture↗

Natural variability of the enantiomeric composition of bioactive chiral terpenes in Mentha piperita.

The variability of the enantiomeric distribution of biologically active chiral terpenes in Mentha piperita plants from different geographical origins was evaluated by solid phase microextraction-gas chromatography-mass spectrometry (SPME-GC-MS). The optimisation of some parameters (i.e. exposure temperature, extraction time and type of fibre) affecting SPME-extraction enabled relative standard deviations ranging from 4 to 13% to be achieved. The use of two different chiral stationary phases allowed to separate the identified chiral terpenes into their corresponding enantiomers as well as to verify the enantiomeric excesses of those compounds which were enantiomerically resolved on both phases. For all chiral terpenes, the enantiomeric composition varied within a very narrow range all over the samples. Consequently, it may be stated that the enantiomeric composition of chiral terpenes in Mentha piperita appears to be independent of the geographical origin of the plant and, thus, any alteration in the characteristic value may be related to an adulteration or inadequate sample handling. These results support the usefulness of the enantiomeric composition of bioactive chiral terpenes in Mentha piperita in authenticity studies.

Mentha piperita↗

[Chemical analysis of bronchoalveolar lavage in diagnostics of pneumonia].

Samples of bronchoalveolar lavages, obtained from 182 patients hospitalised at Vseobecna fakultni nemocnice and Nemocnice Kralovske Vinohrady, Prague, were analysed using solid phase microextraction-gas chromatography. At least 9 %, using less strong criteria up to 20 % of samples, contained higher volatile fatty acids (VFA), indicating the presence of fermenting anaerobic bacteria, found neither by cultivation nor by microscopy. Further compounds appeared in most of chromatographic examinations, tentatively labelled as "alcohol" and "acetoin". The second one occurred almost solely in samples from patients receiving the intensive care including mechanical ventilation. If characterised more precisely, it may serve as a potential marker of patients' status.

Biomarkers↗

[Development and performance evaluation for a solid phase adsorption gas sampler of formaldehyde in indoor air].

OBJECTIVE: We developed a solid phase adsorption gas sampler, which is suitable for collection and analysis of indoor air formaldehyde. METHODS: This solid phase adsorption gas sampler is composed of two parts, a support part made of a glass tube covered silica-gel stopper on ports, an absorbent part in glass tube made of surface denatured synthetic fibre coated formaldehyde absorbent. We evolved its performance, and established an method for sampling and determination formaldehyde in indoor air with the gas sampler. RESULTS: For the solid phase adsorption gas sampler, the collection efficiency was 98.7%, and the desorption efficiency was 98.6%. The variation coefficients of sampling was 4.02% (n = 10). The above method was compared with the standard method (GB/T 16129-1995 ), the results showed no significant difference between the two methods. CONCLUSION: This solid phase adsorption gas sampler can be used for sampling and determination formaldehyde in indoor air.

Air Pollutants↗

Identification and quantification of 77 pesticides in groundwater using solid phase coupled to liquid-liquid microextraction and reversed-phase liquid chromatography.

This paper describes a method for the extraction, separation, identification, and quantification of 77 pesticides (neutral, acidic, and basic) including some s-triazine metabolites. The method is appropriate for organically (e.g. with humic acids) highly loaded groundwater samples. A comparative study of a pH-controlled mixed solid phase (LiChroprep RP18/LiChrolut EN) extraction with different desorption solvents (acetonitrile or acetonitrile and dichloromethane/methanol) is elaborated. A subsequent liquid-liquid microextraction reduces matrix effects. The pesticides in the sample are separated using RP-HPLC, detected, and identified by diode array. The efficiency is illustrated on a natural groundwater sample from a phreatic aquifer.

Chromatography, High Pressure Liquid↗

Sample treatment in chromatography-based speciation of organometallic pollutants.

Speciation analysis is nowadays performed routinely in many laboratories to control the quality of the environment, food and health. Chemical speciation analyses generally include the study of different oxidation state of elements or individual organometallic compounds. The determination of the different chemical forms of elements is still an analytical challenge, since they are often unstable and concentrations in different matrices of interest are in the microg l(-1) or even in the ng l(-1) range (e.g., estuarine waters) or ng g(-1) in sediments and biological tissues. For this reason, sensitive and selective analytical atomic techniques are being used as available detectors for speciation, generally coupled with chromatography for the time-resolved introduction of analytes into the atomic spectrometer. The complexity of these instrumental couplings has a straightforward consequence on the duration of the analysis, but sample preparation to separate and transfer the chemical species present in the sample into a solution to be accepted readily by a chromatographic column is the more critical step of total analysis, and demands considerable operator skills and time cost. Traditionally, liquid-liquid extraction has been employed for sample treatment with serious disadvantages, such as consumption, disposal and long-term exposure to organic solvent. In addition, they are usually cumbersome and time-consuming. Therefore, the introduction of new reagents such as sodium tetraethylborate for the simultaneous derivatization of several elements has been proposed. Other possibilities are based in the implementation of techniques for efficient and accelerated isolation of species from the sample matrix. This is the case for microwave-assisted extraction, solid-phase extraction and microextraction, supercritical fluid extraction or pressurized liquid extraction, which offer new possibilities in species treatment, and the advantages of a drastic reduction of the extraction time and the embodiment into on-line flow analysis systems. This new generation of treatment techniques constitutes a good choice as fast extraction methods for feasible species-selective analysis of organometallic compounds under the picogram level, that can be used for national regulatory agencies, governmental and industrial quality control laboratories, and consequently, for manufacturers of analytical instrumentation.

Chromatography↗

Suitability of hollow fibre liquid-phase microextraction for the determination of acidic pharmaceuticals in wastewater by liquid chromatography-electrospray tandem mass spectrometry without matrix effects.

The applicability of hollow fibre liquid-phase microextraction (LPME), as an alternative to solid-phase extraction (SPE), for the extraction/enrichment of acidic drugs (e.g. ibuprofen, clofibric acid, bezafibrate, etc.) from water samples prior to the determination by LC-ESI-MS-MS has been evaluated. After LPME method optimisation, it was found that this technique can provide very clean extracts, which do not lead to signal suppression during LC-ESI-MS-MS analysis of the analytes. The limits of quantification (0.5-42 ng/L) are suitable for the analysis of these drugs in wastewater. However repeatability needs to been improved (intra-day R.S.D. = 3.4-32%), which may be expected by automation and the development of commercially available devices and fibres specially prepared for analytical purposes. The method was finally applied to wastewater samples (treated and untreated) and results comparable to SPE were obtained.

Chromatography, Liquid↗

Capillary liquid chromatographic determination of cellular flavins.

A capillary LC system was set up and optimized, in which a UV absorbance detector was used and a monolithic silica-ODS column as the separation column. Two on-line concentration techniques, namely, gradient elution mode and in-tube solid-phase ion-pair microextraction (SPIPME), were combined with the capillary LC system, which proved to be beneficial to enhance the concentration sensitivity by enabling the injection of large volumes of samples. The limits of detection at ppb levels for the flavins [riboflavin, flavin mononucleotide (FMN) and flavin adenine dinucleotide (FAD)] were achieved using the two techniques. For in-tube SPIPME, a monolithic silica-ODS column was employed as the extraction column, on which FAD and FMN were retained b y interaction with an ion-pair reagent, tetrabutylammonium phosphate, resulting in greater than 110-fold enhancement in their concentration sensitivities relative to conventional injection method. The reproducibility and linearity of the two methods were investigated. The two methods were applied to analyze trace amounts of flavins in bacterial Escherichia coli cell extracts and recombinant flavoenzymes.

Chromatography, Liquid↗

Determination of pesticides by solid phase extraction followed by gas chromatography with nitrogen-phosphorous detection in natural water and comparison with solvent drop microextraction.

The European Union specifies that drinking water can contain pesticide residues at concentrations of up to 0.1 microg/L each and 0.5 microg/L in total, and that 1-3 microg/L of pesticides can be present in surface water, but the general idea is to keep discharges, emissions and losses of priority hazardous substances close to zero for synthetic substances. Therefore, in order to monitor pesticide levels in water, analytical methods with low quantification limits are required. The method proposed here is based on solid phase extraction (SPE) followed by gas chromatography with a nitrogen-phosphorous detector (GC-NPD). During method development, six organophosphate pesticides (azinphos-ethyl, chlorfenvinphos, chlorpyriphos, ethoprophos, fenamiphos and malathion) and two organonitrogen pesticides (alachlor and deltamethrin) were considered as target analytes. Elution conditions that could influence the efficiency of the SPE were studied. The optimized methodology exhibited good linearity, with determination coefficients of better than 0.996. The analytical recovery for the target analytes ranged from 70 to 100%, while the within-day precision was 4.0-11.5%. The data also showed that the nature of the aqueous matrice (ultrapure, surface or drinking water) had no significant effect on the recovery. The quantification limits for the analytes were found to be 0.01-0.13 microg/L (except for deltamethrin, which was 1.0 microg/L). The present methodology is easy, rapid and gives better sensitivity than solvent drop microextraction for the determination of organonitrogen and organophosphate pesticides in drinking water at levels associated with the legislation.

Chromatography, Gas↗

Multiresidue determination of organophosphorus and organochlorine pesticides in human biological fluids by capillary gas chromatography.

Two multiresidue analytical methods for the simultaneous determination of organophosphorus and organochlorine pesticides in human urine and serum samples are described. The first approach is based on liquid-liquid microextraction with dichloromethane, and the second uses solid-phase extraction with C18. In both methods, the extracts are analyzed by capillary gas chromatography using nitrogen-phosphorus detection (NPD) and electron-capture detection (ECD). Limits of detection of the overall procedure of analysis are at the low ng mL(-1) level. Stability experiments have been performed with spiked urine and serum samples stored at 4 degrees C for 1 month. Finally, the solid-phase extraction procedure was applied to real-world samples. Quantification was performed by NPD or ECD, and peak identity was confirmed by use of mass-selective detection (MSD).

Chromatography, Gas↗

New trend in sample preparation: on-line microextraction in packed syringe for liquid and gas chromatography applications. I. Determination of local anaesthetics in human plasma samples using gas chromatography-mass spectrometry.

A new technique for sample preparation on-line with LC and GC-MS assays was developed. Microextraction in a packed syringe (MEPS) is a new miniaturised, solid-phase extraction technique that can be connected on-line to GC or LC without any modifications. In MEPS approximately 1mg of the solid packing material is inserted into a syringe (100-250 microl) as a plug. Sample preparation takes place on the packed bed. The bed can be coated to provide selective and suitable sampling conditions. The new method is very promising. It is very easy to use, fully automated, of low cost and rapid in comparison with previously used methods. This paper presents the development and validation of a method for microextraction in packed syringe MEPS on-line with GC-MS. Local anaesthetics in plasma samples were used as model substances. The method was validated and the standard curves were evaluated by the means of quadratic regression and weighted by inverse of the concentration: 1/x for the calibration range 5-2000 nM. The applied polymer could be used more than 100 times before the syringe was discarded. The extraction recovery was between 60 and 90%. The results showed close correlation coefficients (R>0.99) for all analytes in the calibration range studied. The accuracy of MEPS-GC-MS was between 99 and 115% and the inter-day precision (n=3 days), expressed as the relative standard deviation (R.S.D.%), was 3-10%.

Anesthetics, Local↗

Microextraction in packed syringe (MEPS) for liquid and gas chromatographic applications. Part II--Determination of ropivacaine and its metabolites in human plasma samples using MEPS with liquid chromatography/tandem mass spectrometry.

A new technique for sample preparation on-line with liquid chromatographic/tandem mass spectrometric (LC/MS/MS) assay was developed. Microextraction in a packed syringe (MEPS) is a new miniaturized, solid-phase extraction technique that can be connected on-line to gas or liquid chromatography without any modifications. In MEPS approximately 1 mg of the solid packing material is inserted into a syringe (100-250 microl) as a plug. Sample preparation takes place on the packed bed. The bed can be coated to provide selective and suitable sampling conditions. The new method is very promising, very easy to use, fully automated, of low cost and rapid in comparison with previously used methods. This paper presents the development and validation of a method for MEPS on-line with LC/MS/MS. Ropivacaine and its metabolites (PPX and 3-OH-ropivacaine) in human plasma samples were used as model substances. The method was validated and the calibration curves were evaluated by means of quadratic regression and weighted by the inverse of the concentration, 1/x, for the calibration range 2-2000 nM. The applied polymer could be used more than 100 times before the syringe was discarded. The extraction recovery was between 40 and 60%. The results showed high correlation coefficients (R(2) > 0.999) for all analytes in the calibration range studied. The accuracy, expressed as a percentage variation from the nominal concentration values, ranged from 0 to 6%. The precision, expressed as the relative standard deviation, at three different concentrations (quality control samples) was consistently about 2-10%. The limit of quantification was 2 nM.

Blood Chemical Analysis↗

Feasibility of a liquid-phase microextraction sample clean-up and liquid chromatographic/mass spectrometric screening method for selected anabolic steroid glucuronides in biological samples.

Anabolic androgenic steroids (AAS) are metabolized extensively in the human body, resulting mainly in the formation of glucuronide conjugates. Current detection methods for AAS are based on gas chromatographic/mass spectrometric (GC/MS) analysis of the hydrolyzed steroid aglycones. These analyses require laborious sample preparation steps and are therefore time consuming. Our interest was to develop a rapid and straightforward method for intact steroid glucuronides in biological samples, using liquid-phase microextraction (LPME) sample clean-up and concentration method combined with liquid chromatographic/tandem mass spectrometric (LC/MS/MS) analysis. The applicability of LPME was optimized for 13 steroid glucuronides, and compared with conventional liquid-liquid extraction (LLE) and solid-phase extraction (SPE) procedures. An LC/MS/MS method was developed for the quantitative detection of AAS glucuronides, using a deuterium-labeled steroid glucuronide as the internal standard. LPME, owing to its high specificity, was shown to be better suited than conventional LLE and SPE for the clean-up of urinary AAS glucuronides. The LPME/LC/MS/MS method was fast and reliable, offering acceptable reproducibility and linearity with detection limits in the range 2-20 ng ml(-1) for most of the selected AAS glucuronides. The method was successfully applied to in vitro metabolic studies, and also tested with an authentic forensic urine sample. For a urine matrix the method still has some unsolved problems with specificity, which should be overcome before the method can be reliably used for doping analysis, but still offering additional and complementary data for current GC/MS analyses.

Anabolic Agents↗

Comparison of microextraction procedures to determine pesticides in oranges by liquid chromatography-mass spectrometry.

A liquid chromatographic-mass spectrometric method has been developed for the determination of bitertanol, carbendazim, fenthion, flusilazole, hexythiazox, imidacloprid, methidathion, methiocarb, pyriproxyfen and trichlorfon. Two procedures, based on stir bar sorptive extraction (SBSE) and matrix solid-phase dispersion (MSPD), have been evaluated for the extraction of these compounds in oranges. Their respective advantages and disadvantages are also discussed. The recoveries obtained by MSPD ranged from 47 to 96% and the relative standard deviations (RSDs) ranged from 1 to 15%, whereas with the SBSE method the recoveries were between 8 and 84% and the RSDs between 4 and 16%. Although, the limits of quantitation of most compounds are much better (0.001-0.05 mg kg(-1)) by SBSE, it is not suitable to determine some polar pesticides as carbendazim, imidacloprid and trichlorfon. Results obtained by both methods were compared, in terms of sensitivity and selectivity, with a classical ethyl acetate extraction method, and the three methods were applied to analyze real samples. As MSPD is easier to perform, faster than the organic solvent extraction, and shows equal accuracy and resolution, its application for analyzing pesticides in oranges is recommended.

Chromatography, Liquid↗

Analysis of persistent organic pollutants in marine sediments using a novel microwave assisted solvent extraction and liquid-phase microextraction technique.

A simple and novel analytical method for quantifying persistent organic pollutants (POPs) in marine sediments has been developed using microwave assisted solvent extraction (MASE) and liquid-phase microextraction (LPME) using hollow fibre membrane (HFM). POPs studied included twelve organochlorine pesticides (OCP) and eight polychlorinated biphenyl (PCB) congeners. MASE was used for the extraction of POPs from 1 g of sediment using 10 ml of ultrapure water at 600 W for 20 min at 80 degrees C. The extract was subsequently subjected to a single step LPME-HFM cleanup and enrichment procedure. Recovery varied between 73 and 111% for OCPs; and 86-110% for PCBs, and exceeded levels achieved for conventional multi-step Soxhlet extraction coupled with solid-phase extraction. The method detection limit for each POP analyte ranged from 0.07 to 0.70 ng g(-1), and peak areas were proportional to analyte concentrations in the range of 5-500 ng g(-1). Relative standard deviations of less than 20% was obtained, based on triplicate sample analysis. The optimized technique was successfully applied to POP analysis of marine sediments collected from the northeastern and southwestern areas of Singapore's coastal environment.

Environmental Monitoring↗

Comparison of simplified methods for pesticide residue analysis. Use of large-volume injection in capillary gas chromatography.

The combination of manual and automated extraction procedures using low sample volumes (5-50 ml) with large-volume oncolumn injection (LVI) (200 microliters) in capillary gas chromatography with flame photometric detection (GC-FPD) has allowed the determination of 16 organophosphorus pesticides in clean water samples at the low ng l-1 level with an important simplification in the sample preparation step. A simple and fast offline liquid-liquid microextraction procedure (2-5 ml water/l ml methyl tert.-butyl ether) has been applied to spiked groundwater samples (containing 0.5 ng of each pesticide) with good recoveries (over 80%) and precision (better than 10%), giving detection limits between 5 and 100 ng l-1 using 200 microliters injections in the GC-FPD system. The application of an inline automated liquid-liquid microextraction-LVI-GC procedure (2 ml water/2 ml methyl tert.-butyl ether: injection of 200 microliters in GC-FPD) using the autosampler ASPEC XL led to lower recoveries (> 50%) as a result of the low efficiency for mixing organic and aqueous phases, although with very satisfactory coefficients of variation (lower than 7%) and detection limits between 20 and 200 ng l-1. Manual and automated solid-phase extraction procedures using the well known C18 cartridges and the new Oasis HLB have been applied to groundwater samples (5-50 ml) spiked with 1 ng of each pesticide. Results obtained for both the manual and the automated procedures were satisfactory (recoveries over 80%) and the limits of detection for 50 ml sample volume ranged from 1 to 6 ng l-1.

Autoanalysis↗

A laboratory technique for investigation of diffusion and transformation of volatile organic compounds in low permeability media.

A laboratory diffusion cell technique that permits spatial and temporal estimates of porewater concentrations over short intervals suitable for estimation of effective diffusion coefficients (De) and degradation rate constants (k) of volatile organic compounds (VOCs) in saturated low permeability media is presented. The diffusion cell is a sealed cylinder containing vapour reservoirs for sampling, including a vapour reservoir source and an array of vapour-filled "mini-boreholes", which are maintained water- and sediment-free by slightly negative porewater pressures. The vapour reservoirs were sampled by Solid Phase Micro-Extraction (SPME), resulting in minimal disturbance to the experimental system. Porewater concentrations are estimated from the measured vapour concentrations. Experiments were conducted using a non-reactive medium and five VOCs with a range in partitioning properties. Calibration experiments showed that equilibrium partition coefficients could be used for calculating concentrations in the vapour reservoir source from concentrations in the SPME coating after a 1-min microextraction and that the reservoir concentration was insignificantly affected by sampling. However, equilibrium was not reached during the one-min extraction of the boreholes; the microextraction reduced the borehole vapour concentrations, leading to diffusion of VOCs from porewater into the vapour-filled borehole. Thus, empirical partitioning coefficients were required for the determination of porewater VOC concentrations. The experimental data and numerical modelling indicate masses extracted by SPME extraction are relatively small, with minimal perturbation on processes studied in diffusion experiments. This technique shows promise for laboratory investigation of diffusion and transformation processes in low permeability media.

Carbon Disulfide↗