RESUMEN
This review focuses on the applications of silicone in the form of tubes or rods for sorptive extraction of organic compounds as sample preparation method in combination with various chromatographic techniques. Silicone rods (SRs) and silicone tubes (STs) have the advantage of being inexpensive, flexible and robust. SRs and STs with different sizes and volumes of silicone (8-635microL) have so far been applied for the extraction/preconcentration of a large variety of organic micropollutants from different matrices. The theoretical principle of SR and ST extraction in comparison with similar microextraction techniques is presented as well as a summary of the published applications of SR and ST extraction in combination with gas chromatography (GC) or liquid chromatography (LC). Furthermore, the use of SRs and STs for time-integrated (passive) sampling is reported.
Asunto(s)
Fraccionamiento Químico/instrumentación , Fraccionamiento Químico/métodos , Siliconas/química , Adsorción , Aire/análisis , Cromatografía de Gases , Modelos Teóricos , Agua/químicaRESUMEN
This work describes the application of two sample preparation methods: membrane-assisted solvent extraction (MASE) and solid phase extraction (SPE) in combination with high performance liquid chromatography-tandem mass spectrometry (HPLC-MS-MS) for the determination of 10 pesticides in surface and ground water. Optimal extraction conditions for MASE were 60 min extraction time at 30 degrees C with a solvent volume of 100 microL toluene. 5 microL of the toluene extract were directly injected in the HPLC-MS-MS system. Concerning SPE, two materials were tested and C18 was superior to Oasis HLB. Complete desorption was ensured by desorbing the SPE (C18) cartridge with 3 mL of an acetonitrile/methanol mixture (1:1). After evaporation, the extract was injected in the analytical system. Analyte breakthrough was not found for the investigated compounds. For both methods, high extraction yields were achieved, in detail 71% (metalaxyl) till 105% (linuron) for MASE and 52% (ethiofencarb) till 77% (prometryne) for SPE (C18). Detection limits were in the low ng/L range for both methods and precision, expressed as the relative standard deviation (RSD) of the peak areas was below 13%. Five real water samples were analyzed applying both extraction methods. The results were in good agreement and standard addition proved that no matrix effects (such as ion suppression) occurred. In this comparison SPE has the potential of larger sensitivity whereas faster analysis and slightly better recoveries were achieved with MASE. MASE shows potential to be a promising alternative to the conventional off-line SPE concerning low to medium polar compounds.
Asunto(s)
Cromatografía Líquida de Alta Presión/métodos , Plaguicidas/análisis , Extracción en Fase Sólida/métodos , Espectrometría de Masas en Tándem/métodos , Contaminantes Químicos del Agua/análisis , Interpretación Estadística de Datos , Agua Dulce/química , Concentración de Iones de Hidrógeno , Membranas Artificiales , Reproducibilidad de los Resultados , Sensibilidad y Especificidad , Cloruro de Sodio/química , Solventes/química , Temperatura , Tolueno/químicaRESUMEN
A new approach for headspace sorptive extraction is presented and demonstrated for the determination of 12 chlorobenzenes in water samples. It consists of a silicone tube (15-mm length) arranged around a stainless steel rod. This device is fixed on a septum cap and exposed to the headspace of 50 mL of a salt-saturated water sample. After extraction (60-min optimized extraction time), thermodesorption is carried out by direct insertion of the silicone tube into the thermodesorption-gas chromatography-mass spectrometry system. Desorption of the analytes is performed at 250 degrees C for 5 min with a gas flow of 50 mL/min. Repeatability (relative standard deviation 5-10%), extraction yields (9-46%), enrichment factors (129-657), and detection limits (0.002-0.012 microg/L) were determined and four real water samples were analyzed with the headspace tube extraction. The results were verified by standard addition. A comparison of headspace tube extraction with other headspace enrichment techniques underlined the high extraction capacity of the proposed method. A big advantage of tube extraction is the low cost of the silicone material. The tubes can be discarded after single use, avoiding carryover problems and cross-contamination.
Asunto(s)
Fraccionamiento Químico/instrumentación , Clorobencenos/análisis , Siliconas/química , Contaminantes Químicos del Agua/análisis , Adsorción , Fraccionamiento Químico/métodos , Clorobencenos/química , Cromatografía de Gases y Espectrometría de Masas , Reproducibilidad de los Resultados , Sensibilidad y Especificidad , Propiedades de Superficie , Factores de Tiempo , Volatilización , Contaminantes Químicos del Agua/químicaRESUMEN
Membrane-assisted solvent extraction (MASE) in combination with large volume injection-gas chromatography-mass spectrometry (LVI-GC-MS) was applied for the determination of 16 polycyclic aromatic hydrocarbons (PAHs) in aqueous samples. The MASE conditions were optimized for achieving high enrichment of the analytes from aqueous samples, in terms of extraction conditions (shaking speed, extraction temperature and time), extraction solvent and composition (ionic strength, sample pH and presence of organic solvent). Parameters like linearity and reproducibility of the procedure were determined. The extraction efficiency was above 65% for all the analytes and the relative standard deviation (RSD) for five consecutive extractions ranged from 6 to 18%. At optimized conditions detection limits at the ng/L level were achieved. The effectiveness of the method was tested by analyzing real samples, such as river water, apple juice, red wine and milk.
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Bebidas/análisis , Cromatografía de Gases y Espectrometría de Masas/métodos , Hidrocarburos Policíclicos Aromáticos/análisis , Solventes/química , Agua/química , Fraccionamiento Químico/métodos , Hidrocarburos Policíclicos Aromáticos/química , Reproducibilidad de los ResultadosRESUMEN
This work describes a novel, simple, and inexpensive approach for an absorptive extraction of organic contaminants from aqueous samples applying polysiloxane tubes. After the extraction, the tubes were desorbed with 200 microL of an organic solvent and 50 microL of the extract were transferred via large volume injection (LVI) into a gas chromatography-mass spectrometry system (GC-MS). Fourteen organic compounds covering a broad range in polarity with log K(o/w)-values between 2.6 (atrazine) and 7 (polychlorinated biphenyl 138, PCB 138) were chosen as model compounds. The experimental parameters affecting the efficiency of the process such as desorption solvents, the addition of salt and pH-change, the extraction and desorption time were carefully optimised. The recoveries were compared with theoretical values. The limits of detection (LODs) were in the range of 0.5-5 ng/L and the precision was 7-15%. The method was successfully applied to the analysis of a contaminated river water sample.
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Dimetilpolisiloxanos/química , Cromatografía de Gases y Espectrometría de Masas/métodos , Compuestos Orgánicos/análisis , Siliconas/química , Microextracción en Fase Sólida/métodos , Contaminantes Químicos del Agua/análisis , Reproducibilidad de los Resultados , IncertidumbreRESUMEN
A novel and simple approach to sorptive materials for the extraction of organic compounds from environmental samples is presented. It entails the use of glass fiber fabric strips coated with a customized poly(acrylate) (PA) formulation as extraction medium. Analytes were enriched by means of shaking of the PA strip in the sample and then subsequently thermally desorbed and analyzed by GC-MS. The performance of the sorptive materials was evaluated by the enrichment of compounds with different polarities (phenols, hexachlorobenzene and hexachlorocyclohexanes) from water samples. Parameters that affect the extraction process such as pH, ionic strength of the solvent, mixing mechanism, extraction time and desorption conditions were investigated. The extraction abilities of the PA extraction medium were compared with that of commercially available poly(dimethylsiloxane) (PDMS) Twisters. The results revealed that the new material shows higher affinity for phenolic compounds presumably due to the presence of polar groups. The partition coefficients for the PA strips estimated in this work were up to 15 times higher than for the PDMS Twister, resulting in higher recoveries and lower detection limits. The method was applied for the quantification of the aforementioned compounds in contaminated surface water samples from Bitterfeld (Germany). Using both PA strips and PDMS Twisters, good agreement of the extraction data was achieved.
Asunto(s)
Dimetilpolisiloxanos/química , Vidrio/química , Contaminantes Químicos del Agua/aislamiento & purificación , Cromatografía de Gases y Espectrometría de Masas , Concentración de Iones de Hidrógeno , Factores de Tiempo , Purificación del Agua/métodosRESUMEN
The new membrane-enclosed silicone collector (MESCO) was, in two different configurations with respect to the thickness of low-density polyethylene membrane used, subject to serial batch extraction tests to obtain (preliminary) sampling rates for estimating water concentrations of selected chlorinated organic compounds and polycyclic aromatic hydrocarbons. This rapid calibration procedure is simple to implement compared to experiments in a flow-through apparatus and yielded reasonable sampling rates in the range of 50 microL-2 mL per hour for the compounds tested. The new MESCO formats were also exposed for 28 days in the polluted creek to test their field performance. For priority contaminants of special interest, alpha-hexachlorocyclohexane and hexachlorobenzene, the time-weighted average concentrations derived from the freshly calibrated sampling devices agree well with those obtained by conventional water analysis of spot samples.
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Calibración , Membranas Artificiales , Siliconas/química , Contaminantes Químicos del Agua/análisisRESUMEN
An analytical method for the determination of several organochlorine pesticides (OCPs) like hexachlorocyclohexanes (HCHs), cyclodiene derivates (dieldrin, aldrin, endrin, heptachlor, heptachlor epoxide, endrin aldehyde, endosulfan and ensodulfan sulphate) and DDX compounds (p,p'-DDE, p,p'-DDD and p,p'-DDT) as well as chlorobenzenes in soils has been developed. The procedure is based on pressurized subcritical water extraction (PSWE) followed by stir bar sorptive extraction (SBSE) and subsequent thermodesorption-gas chromatography/mass spectrometry analysis. Significant PSWE and SBSE parameters were optimized using spiked soil and water samples. For the PSWE of the organochlorine compounds, water modified with acetonitrile as the extraction solvent, at an extraction temperature of 120 degrees C, and three cycles of 10 min extraction proved to be optimal. Under optimized conditions, the figures of merit, such as precision, accuracy and detection limits were evaluated. The detection limits obtained for soil samples were in the range 0.002-4.7 ng/g. Recoveries between 4.1 and 85.2% were achieved from samples spiked at a concentration level of 25-155 ng/g. The main advantages of this method are the avoidance of clean-up and concentration procedures as well as the significant reduction of the required volume of organic solvents. The described method was applied to the determination of the pollutants in soil samples collected from a polluted area, the Bitterfeld region (Germany). The results obtained by PSWE-SBSE were in a good agreement with those obtained by a reference method, a conventional pressurized liquid extraction (PLE).
Asunto(s)
Hidrocarburos Clorados/análisis , Plaguicidas/análisis , Contaminantes del Suelo/análisis , Cromatografía de Gases y Espectrometría de Masas , PresiónRESUMEN
In this paper the determination of Ochratoxin A (OTA) in low volumes of human blood serum by enzyme-linked immunosorbent assay (ELISA) is compared with an appropriate capillary electrophoresis with laser-induced fluorescence detection (CE-LIF) method. In order to use ELISA for high-throughput analysis in epidemiological studies no sample cleanup was performed. Both methods showed a limit of detection (LOD) of 0.5 ng/mL. Comparing the precisions of both methods, the data show that the quantified concentrations in ELISA are higher than the corresponding concentrations in the CE-LIF method. Using a matrix calibration curve instead of a standard calibration curve the reproducibilities of both methods are comparable. No additional matrix effect could be observed by adding phenylalanine as probable matrix compound to the serum.
Asunto(s)
Electroforesis Capilar/métodos , Ensayo de Inmunoadsorción Enzimática/métodos , Ocratoxinas/sangre , Espectrometría de Fluorescencia/métodos , Calibración , Humanos , Ocratoxinas/química , Fenilalanina/química , Reproducibilidad de los Resultados , SueroRESUMEN
The present work compares two modern and environmentally friendly enrichment techniques, stir bar sorptive extraction (SBSE) and membrane-assisted solvent extraction (MASE) for the determination of 18 organic contaminant residues in Brazilian sugarcane juice. Stir bar sorptive extraction and thermal desorption coupled to capillary gas chromatography-mass spectrometry using the selected ion monitoring mode [SBSE-TD-GC-MS(SIM)] and membrane-assisted solvent extraction combined with large volume injection [MASE-LVI-GC-MS(SIM)] methods were assessed taking into account the time of extraction [SBSE (3h) and MASE (30min)], the recoveries [SBSE (0.2-55.3%) and MASE (13.6-103.1%)], the repeatability [SBSE (0.3-19.2%) and MASE (2.6-18.4%)] and the limits of detection [SBSE (0.002-0.71 microgL(-1)) and MASE (0.004-0.56 microgL(-1))] of the selected triazine, organochlorine and organophosphorus pesticides as well as benzo[a]pyrene in sugarcane juice. In general, faster analyses and much better analyte recovery results were achieved with MASE, whereas greater sensitivity and repeatability were obtained with SBSE. SBSE and MASE procedures were applied to the analysis of six sugarcane juice samples from the city São Carlos, in the state of São Paulo, Brazil. A comparison of the results of the pesticide and benzo[a]pyrene residues at microgL(-1) level obtained by the two methods showed good agreement.
Asunto(s)
Benzo(a)pireno/análisis , Fraccionamiento Químico/métodos , Cromatografía de Gases y Espectrometría de Masas/métodos , Residuos de Plaguicidas/análisis , Saccharum/química , Bebidas/análisis , Hexaclorobenceno/análisis , Triazinas/análisisRESUMEN
Membrane-enclosed sorptive coating (MESCO) is a miniaturised monitoring device that enables integrative passive sampling of persistent, hydrophobic organic pollutants in water. The system combines the passive sampling with solventless preconcentration of organic pollutants from water and subsequent desorption of analytes on-line into a chromatographic system. Exchange kinetics of chemicals between water and MESCO was studied at different flow rates of water, in order to characterize the effect of variable environmental conditions on the sampler performance, and to identify a method for in situ correction of the laboratory-derived calibration data. It was found that the desorption of chemicals from MESCO into water is isotropic to the absorption of the analytes onto the sampler under the same exposure conditions. This allows for the in situ calibration of the uptake of pollutants using elimination kinetics of performance reference compounds and more accurate estimates of target analyte concentrations. A field study was conducted to test the sampler performance alongside spot sampling. A good agreement of contaminant patterns and water concentrations was obtained by the two sampling techniques.
Asunto(s)
Monitoreo del Ambiente/instrumentación , Hidrocarburos Clorados/análisis , Contaminantes Químicos del Agua/análisis , Adsorción , Calibración , Monitoreo del Ambiente/métodos , Análisis de Inyección de Flujo/instrumentación , Análisis de Inyección de Flujo/métodos , Miniaturización , Propiedades de SuperficieRESUMEN
Solid phase microextraction (SPME) fibres coated with Carbowax/divinylbenzene and semi-permeable membrane devices (SPMDs) of standard configuration were used to obtain time-weighted average (TWA) field air concentrations of selected chlorinated semi-volatile compounds on a landfill, where large amounts of lindane by-products were deposited, together with other hazardous chemical residues in the past. Additionally, spot sampling with SPME fibres was performed to identify the emission hotspot and sampling rates were determined/predicted for the substances of interest. Both samplers yield comparable TWA air concentrations of lindane and its isomers and of DDT with its metabolites and gain in certainty about the landfill as remaining source of air pollution with these compounds in the region. Both SPME fibres and SPMDs (respective their modifications) can be recommended as sampling tools in process studies and larger air monitoring programmes. However, further calibration studies and field tests are necessary to obtain reliable sampling rates for a wider range of semi-volatile compounds.
Asunto(s)
Contaminantes Atmosféricos/análisis , Monitoreo del Ambiente/instrumentación , Hidrocarburos Clorados/análisis , DDT/análisis , Monitoreo del Ambiente/métodos , Diseño de Equipo , Gases , Alemania , Residuos Peligrosos , Hexaclorociclohexano/análisis , Humanos , Residuos de Plaguicidas/análisis , Eliminación de ResiduosRESUMEN
A new module of membrane-assisted solvent extraction (MASE) with miniaturized membrane bags was applied to the determination of seven volatile organic compounds (VOCs): chloroform, 1,1,1-trichloroethane, trichloroethylene, 1,1,2-trichloroethane, tetrachloroethene, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane with boiling points between 61 and 147 degrees C in aqueous samples. Different from the known procedure the new, shortened membrane bags were filled with 100 microl of an organic solvent. The membrane bags were placed in a 20 ml headspace vial and filled with 15 ml of the aqueous sample. The vial was transferred into an autosampler where it was stirred for a definite time at elevated temperature. After the extraction, 1 microl of the organic extract was transferred into the spilt/splitless injector of a GC system equipped with an electron-capture detector. This work included optimization of the membrane device, the determination of the optimized extraction conditions such as stirring rate, extraction time and the impact of salt addition. The validation of the method involved repeatability, recovery and detection limit studies, followed of its application towards real water samples. The repeatability, expressed as the relative standard deviation of the peak areas of six extractions was below 10%. The detection limits (LODs) were between 5 ng/l (tetrachloroethene) and 50 ng/l (chloroform). Calibration was performed in a range from 5 ng/l to 150 microg/l, since the concentration in the aqueous samples was expected quite various in this concentration range. Five river water samples of Bitterfeld, Saxony-Anhalt, Germany were analyzed with miniaturized-MASE and the results were compared with those obtained with Headspace-Analysis. The method can be fully automated and moreover, it allows the simultaneous determination of volatile and semi volatile compounds.
Asunto(s)
Cromatografía de Gases/métodos , Hidrocarburos Clorados/análisis , Hipofisectomía Química/métodos , Contaminantes Químicos del Agua/análisis , Electrones , Cromatografía de Gases y Espectrometría de Masas/métodos , Hipofisectomía Química/instrumentación , Membranas Artificiales , VolatilizaciónRESUMEN
Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the environment; they are of concern due to their toxic properties. Anthropogenic activities could contribute in a significant way to the total burden of PAHs in remote mountain areas. In this work, we document the analysis of PAHs deposition through sedimentary records obtained in three remote Andean lakes located in south central Chile. Sediment cores were taken in one of the deepest sections of each lake, ranging from 45 to 135 m depth. Sediments were carefully extruded in 1-cm layers for PAHs and dating analysis (210Pb and 137Cs). Sixteen Environmental Protection Agency prioritary PAHs were analyzed using high-performance liquid chromatography with fluorescence detection. Dating of sediments was possible for only two lakes (Laja and Galletue). The superficial composition of PAHs in each lake is rather similar with a characteristic dominance of perylene; levels ranged 355 to 3050 ng g(-1) d.w. Depositional fluxes averaged 118 microg m2 year(-1) in Laja Lake in contrast to that in Galletue Lake, where average fluxes reach 434 microg m2 year(-1). Dating back to 50 years, PAH profiles did not experience drastic changes despite the rapid development of industrialization over the past 30 years in the surrounding region, indicating that levels and composition remains fairly similar to those of the present. Finally, determined fluxes were in the lower range of depositional fluxes calculated for lakes located in the industrialized northern hemisphere.
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Sedimentos Geológicos/análisis , Hidrocarburos Policíclicos Aromáticos/análisis , Contaminantes Químicos del Agua/análisis , Altitud , Radioisótopos de Cesio , Chile , Monitoreo del Ambiente , Agua Dulce , Radioisótopos de PlomoRESUMEN
This paper reports the occurrence of polyaromatic hydrocarbons (PAHs) deposition inferred from a sediment core of an Andean lake in south central Chile. Sediments were carefully collected from one of the deepest section of the lake and sliced every 1 cm. The samples were analyzed for PAHs, (137)Cs, (210)Pb, organic carbon and grain-size. The stratigraphic chronology and the sedimentation rates were estimated using the sedimentary signature left by the (137)Cs and (210)Pb fallout as temporal markers. PAHs were quantified by HPLC-fluorescence detection (HPLC-Fluorescence). 15 priority EPA PAHs were analyzed in this study. Based on these results, PAH deposition over the last 50 years was estimated (a period characterized by an important intervention in the area). PAH concentration ranged from 226 to 620 ng g(-1) d.w. The highest concentrations of PAHs were found in the core's bottom. The PAH profile is dominated by the presence of perylene indicating a natural source of PAH. In addition, two clear PAH deposition periods could be determined: the most recent with two-four rings PAHs, the older one with five-seven rings predomination. Determined fluxes where 71 to 972 microg m(-2) year(-1), dominated by perylene deposition. PAH levels and fluxes are lower compared to the levels found in sediments from remote lakes in Europe and North America. It is concluded that the main source of PAHs into the Laja Lake sediments are of natural origin.
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Sedimentos Geológicos/análisis , Hidrocarburos Policíclicos Aromáticos/análisis , Contaminantes Químicos del Agua/análisis , Carbono/análisis , Chile , Monitoreo del Ambiente , Agua Dulce , Radioisótopos de Plomo , Nitrógeno/análisis , Tamaño de la PartículaRESUMEN
Membrane-assisted solvent extraction (MASE) was applied for the determination of seven phenols (phenol, 2-chlorophenol, 2,4-dimethylphenol, 2,4-dichlorophenol, 4-chloro-3-methylphenol, 2,4,6-trichlorophenol and pentachlorophenol) with log Kow (octanol-water-partition-coefficient) between 1.46 (phenol) and 5.12 (pentachlorophenol) in water. The extraction solvents cyclohexane, ethyl acetate and chloroform were tested and ethyl acetate proved to be the best choice. The optimisation of extraction conditions showed the necessity of adding 5 g of sodium chloride to each aqueous sample to give a saturated solution (333 g/L). The pH-value of the sample was adjusted to 2 in order to convert all compounds into their neutral form. An extraction time of 60 min was found to be optimal. Under these conditions the recovery of phenol, the most polar compound, was 11%. The recoveries of the other analytes ranged between 42% (2-chlorophenol) and 98% (2,4-dichlorophenol). Calibration was performed using large volume injection (100 microL injection volume). At optimised conditions the limits of detection were between 0.01 and 0.6 microg/L and the relative standard deviation (n = 3) was on average about 10%. After the method optimisation with reagent water membrane-assisted solvent extraction was applied to two contaminated ground water samples from the region of Bitterfeld in Saxony-Anhalt, Germany. The results demonstrate the good applicability of membrane-assisted solvent extraction for polar analytes like phenols, without the necessity of derivatisation or a difficult and time-consuming sample preparation.
Asunto(s)
Cromatografía de Gases y Espectrometría de Masas/métodos , Fenoles/aislamiento & purificación , Automatización , Clorofenoles/aislamiento & purificación , Concentración de Iones de Hidrógeno , Sensibilidad y Especificidad , Cloruro de Sodio , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/aislamiento & purificaciónRESUMEN
Lipid-filled semipermeable membrane devices (SPMDs) are receiving increasing attention as passive, in situ samplers for the assessment of environmental pollutant exposure. Although SPMDs have been successfully used in a variety of field studies in surface waters, only a few studies have addressed their characteristics as groundwater samplers. In this study, the performance of the SPMDs for monitoring organic contaminants in groundwater was evaluated in a pilot field application in an area severely contaminated by chemical waste, especially by chlorinated hydrocarbons. The spatial distribution of hydrophobic groundwater contaminants was assessed using a combination of passive sampling with SPMDs and non-target semiquantitative GC-MS analysis. More than 100 contaminants were identified and semiquantitatively determined in SPMD samples. Along the 6 field sites under investigation, a large concentration gradient was observed, which confirms a very limited mobility of hydrophobic substances in dissolved form in the aquifer. The in situ extraction potential of the SPMD is limited by groundwater flow, when the exchange volume of well water during an exposure is lower than the SPMD clearance volume for the analytes. This study demonstrates that SPMDs present a useful tool for sampling and analyzing of groundwater polluted with complex mixtures of hydrophobic chemicals and provides guidance for further development of passive sampling technology for groundwater.
Asunto(s)
Monitoreo del Ambiente/instrumentación , Contaminantes del Suelo/análisis , Contaminantes Químicos del Agua/análisis , Ensayo de Materiales , Membranas Artificiales , Compuestos Orgánicos/análisis , PermeabilidadRESUMEN
Two new types of passive samplers were designed and tested on semivolatile organic compounds. The first type (a spiral-rod sampler) consists of a low-density polyethylene membrane acting as a permeation film and a silicone elastomer as the receiving material; the second (a stir-bar sampler) has the same membrane material but a polydimethylsiloxane-coated stir bar acting as the collector phase and installed radially symmetrically in the sampler. The advantages of the new samplers are their simple design, low costs, and their easy processing via thermodesorption coupled with capillary gas chromatography and mass selective detection. In both samplers, the uptake of selected analytes was integrative over exposure periods of up to 384 h. The sampling rates calculated from a laboratory calibration study using the chlorinated semivolatiles hexachlorobenzene, hexachlorocyclohexane isomers and polychlorinated biphenyls ranged from 88.1 ml h-1 for delta-hexachlorocyclohexane to 3443 ml h-1 for 2,2',5,5'-tetrachlorobiphenyl. A field trial at a hazardous waste dump near Bitterfeld, Germany, for up to 21 days combined with periodical determinations of air concentrations using low-volume sampling indicated that the new samplers can in principle be used in the field, although the sampling rates derived from the field results differed considerably from the laboratory findings. Nevertheless the preliminary results suggest that the new sampler types are promising for the long-term air monitoring of semivolatiles.
Asunto(s)
Contaminantes Atmosféricos/análisis , Monitoreo del Ambiente/instrumentación , Hidrocarburos/análisis , Calibración , Diseño de Equipo , VolatilizaciónRESUMEN
In this study the levels and distribution of some persistent toxic substances (PTS) were investigated in soils, superficial water, and snow along an altitudinal gradient in the Laja River Basin (South Central Chile). The principal objective was to establish the basin's contamination status. The working hypothesis was that PTS levels and distribution in the basin are dependent on the degree of anthropogenic intervention. Fifteen PAHs, seven PCBs congeners, and three organochlorine pesticides were studied in superficial soil and water samples obtained along the altitudinal gradient and from a coastal reference station (Lleu-Lleu River). Soil samples were extracted using accelerated solvent extraction with acetone/cyclohexane (1:1) for PAHs and organochlorine compounds. Contaminants were extracted from water and snow samples by liquid-liquid extraction (LLE). PAH and organochlorine compound quantification was carried out by HPLC with fluorescence detection and GC-MS, respectively. PCBs in soils presented four different profiles in the altitudinal gradient, mainly determined by their chlorination degree; these profiles were not observed for the chlorinated pesticides. In general, the detected levels for the analyzed compounds were low for soils when compared with soil data from other remote areas of the world. Higher summation operator PAHs levels in soils were found in the station located at 227 masl (4243 ng g-1 TOC), in a forestry area and near a timber industry, where detected levels were up to eight times higher than the other sampling sites. In general, PAH levels and distribution seems to be dependent on local conditions. No pesticides were detected in surface waters. However, congeners of PCBs were detected in almost all sampling stations with the highest levels being found in Laja Lake waters, where 1.1 ng/l were observed. This concentration is two times higher than values reported for polluted lakes in the Northern Hemisphere. The presence of organochlorine compound in snow sampled at the highest elevation point of the basin is indicative of the transport and atmospheric deposition phenomena of alpha-HCH, gamma-HCH and PCB 52, with values being similar to the levels reported in Canadian snow samples. We conclude that environmental PTS substance levels are in general relatively low, although PAHs may be of concern in some areas of the basin.
Asunto(s)
Contaminantes Ambientales/análisis , Bifenilos Policlorados/análisis , Hidrocarburos Policíclicos Aromáticos/análisis , Contaminantes del Suelo/análisis , Contaminantes Químicos del Agua/análisis , Altitud , Chile , Monitoreo del Ambiente , RíosRESUMEN
A simple procedure based on stir bar sorptive extraction (SBSE) and high-performance liquid chromatography-fluorescence detection (HPLC-FLD) is presented for the determination of 15 polycyclic aromatic hydrocarbons (PAHs) in herbal tea prepared with Mate leaves (Ilex paraguariensis St. Hil.). The influence of methanol and salt addition to the samples, the extraction time, the desorption time and the number of desorption steps, as well as the matrix effect, were investigated. Once the SBSE method was optimised (10 mL of Mate tea, 2h extraction at room temperature followed by 15 min desorption in 160 microL of an acetonitrile (ACN)-water mixture), analytical parameters such as repeatability (< or = 10.1%), linearity (r2 > or = 0.996), limit of detection (LOD, 0.1-8.9 ng L(-1) ), limit of quantitation (LOQ, 0.3-29.7 ng L(-1) and absolute recovery (24.2-87.0%) were determined. For calibration purposes, a reference sample was firstly obtained by removing the analytes originally present in the lowest contaminated Mate tea studied (via SBSE procedure) and then spiked at 1-1200 ng L(-1)range. The proposed methodology proved to be very convenient and effective, and was successfully applied to the analysis of 11 Mate tea samples commercialised in Brazil. The results of the commercial Mate tea samples found by the SBSE approach were compared with those obtained by liquid-liquid extraction (LLE), showing good agreement.