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1.
In a surface water screening, 30 representative surface water samples collected from rivers, canals, and lakes in Berlin were investigated for the presence of 22 substituted phenols. The phenols selected include the 11 phenols considered as “priority pollutants” by the US Environmental Protection Agency (US-EPA). Surface water samples were extracted applying solid-phase extraction with styrenedivinylbenzene adsorbent. The recoveries, determined in spiking experiments, were between 80 % and 103 %. After derivatization with N-(tert-butyldimethylsilyl)-N-methyl-trifluoroacetamide (MTBSTFA) the samples were analyzed by capillary gas chromatography-mass spectrometry (GC-MS). Phenol, cresols, 2-ethylphenol, 2-chlorophenol, 4-chloro-3-methylphenol, pentachlorophenol, 2-nitrophenol, and 4-nitrophenol were detected in the surface water samples at concentrations between 0.02 μg/L and 7.8 μg/L, respectively. The distribution of these residues in the Berlin surface waters showed that the phenolic residues, with the exception of pentachlorophenol and 2-ethylphenol, do not originate primarily from municipal sewage treatment plants discharges. Some of the phenols are formed naturally or occur as ubiquitous anthropogenic contaminants in the aquatic system.  相似文献   

2.
GC/MS Nontarget Analysis to Examine an Organic Groundwater Contamination. Part I: Sampling – Analysis – Identification GC/MS nontarget analysis is a combination of an extraction sequence and a GC/MS analysis without standards. The extraction sequence should enrich a wide range of organic substances with different chemical and physical properties. The GC/MS analysis without standards evaluates the total chromatogram whereas the possibilities of compound identification are limited. This kind of view is suited very well if the task of examinations are unknown organic contaminations and the conventional target analysis has to be expanded to a large number of compounds with the uncertainty of detecting the main contaminants. The extraction sequence is similar to the EPA 625 analysis of base/neutral and acid extractable organic compounds. Basis are liquid extraction and solid-phase extraction at different pH values. This extraction procedure covers approximately 30 % of total organic carbon of these groundwater samples from a contaminated area near a low temperature carbonization plant. Relevant groups of organic compounds analyzed in the contaminated groundwater or in the reference sample are substituted aromatics, phenols, benzoamines (anilines), and derivates of benzothiophene. Differences in the trace substance mixtures between the contaminated samples and the reference sample are demonstrated by applying modern graphical methods.  相似文献   

3.
In the present work, experiments have been carried out with a focus to reduce the volume requirement of solvent by mixing with imidazolium based ionic liquids (ILs) for the solvent extraction of phenol, p‐chlorophenol, 2,4‐dichlorophenol, 2,4,6‐trichlorophenol, and pentachlorophenol from aqueous solutions. The effect of aqueous phase pH (2–12), agitation speed (100–450 rpm), solute concentration in feed (2–50 mg/L), temperature (303–333 K), treat ratio (1–11), and 1‐butyl‐3‐methyl imidazolium tetrafluoroborate [Bmim]+[BF4]? volume in tributyl phosphate (TBP; 0–0.7% v/v) on extraction of phenols has been studied and optimized. Parameters like strip phase pH (3–13) and stripping agent concentration (0.001–0.009 N) have also been studied for stripping of phenols from solvent phase. It has been found that 0.5% v/v of ionic liquid [Bmim]+[BF4]? in solvent TBP extracts more than 97.5% of phenol and chlorophenols from aqueous solutions with a treat ratio (aqueous to solvent phase ratio) of 5. Transport mechanism for extraction and stripping of phenol and chlorophenols using ionic liquid [Bmim]+[BF4]? has been discussed. The results show that by appropriate selection of extraction and stripping conditions, it is possible to remove nearly all phenols with a treat ratio of 5.  相似文献   

4.
The separation of heavy metals by complexation with macromolecular water-soluble agents and subsequent ultrafiltration is described. The method can be expected to join common techniques of metal separation like liquid-liquid extraction, adsorption, redox reaction or liquid membrane permeation. Reactions between metal ions and polymer phases are characterized as pH-dependent distribution equilibria illustrated at a propene-maleic acid copolymer as an example. The complexation behaviour of the substance under study is governed by isotherms of the saturation type. Attempts proved to be successful to calculate break-through constants as well as saturation capacities from batch-type studies and dynamic measurements by transferring the laws of adsorption and ion exchange, respectively, to the ultrafiltration process. The quantities of fixed metals amounting to about 2.5 mmol/g were found to be in the range of moderate adsorbents. A solution consisting of 3 solutes has been tested to get more detailed information on mixture behaviour as compared to single component systems. In the long run, the proposed method should provide an additional variant for the extraction and concentration of metal ions from diluted aqueous solutions.  相似文献   

5.
Mobilization Potential of Hydrophobic Organic Compounds (HOCs) in Contaminated Soils and Waste Materials. Part II: Mobilization Potential of PAHs, PCBs, and Phenols by Natural Waters To evaluate the hazard potential of organic pollutants in a soil, the mobilization potential of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and phenol derivatives in different waters was ascertained by elution experiments and compared to common elution procedures. Furthermore, dissolved organic matter from different sources was examined with regard to its influence on solubility. The results of the elutions pointed out that depending on the composition of the water sample, the leaching behaviour of the PAHs and PCBs is very different and is determined not only by the concentration of the dissolved organic carbon (DOC) but particularly by its quality. The separation of DOC-associated and “free” dissolved pollutants with the solid-phase extraction on C18-reversed phases revealed the responsibility of the sorption of the pollutants to the DOC for their solubility and mobilization. Moreover, an increase of association of pollutants to the DOC was observed with growing hydrophobicity corresponding to their octanol/water partition coefficient Kow. The comparison of the elutions showed that the exclusively used S4-elution (German standard DIN 38414 part 4) is not appropriate to evaluate the mobilization of hydrophobic organic pollutants realistically. The eluted PAHs (PCBs) of the S4-elution were exceeded in landfill leachate by a factor of 7 (7), in the pond water by a factor of 9 (15), and in the compost saturation extract even by a factor of 35 (56). In contrast, a realistic “worst-case” leaching could be simulated with a tensidic SDS-solution corresponding to an elution process evaluating the mobilization of organic pollutants. The DOC of real waters and surfactants has little influence on the mobilization of the comparatively polar phenols. Concerning a “worst-case” evaluation of mobilization, the S4-elution under alkaline conditions is doubtlessly useful for water-soluble phenols.  相似文献   

6.
Artefact-free Determination of Trihalomethanes in Chlorinated Swimming-pool Water Using Headspace Solid-phase Microextraction and Gas Chromatography Headspace solid-phase microextraction (headspace SPME) is a rather new technique for the solvent-free extraction and concentration of volatile substances from water into an organic polymer layer covering a fused-silica fiber. In combination with gas chromatography, the method represents a powerful tool for sensitive headspace investigations. As the adsorption of low boiling substances is favoured at low temperatures, the method can be operated at ambient temperature without formation of artefacts. Therefore, the method is ideally suited for the analysis of volatile disinfection by-products in water including several thermolabile THM-precursors. For the artefact-free determination of trihalomethanes it is superior to headspace gas chromatography under the conditions of the German standard method DIN 38407-F5. Compared to gas chromatography after pentane extraction (DIN 38407-F4), headspace SPME is simpler, less- laborious, better reproducible, and, especially for polar, easily water-soluble components, much more sensitive. In addition, it operates solvent-free and can be automated. Using a 100-μ polydimethylsiloxane-coated fiber, the method is linear over at least 2 orders of magnitude and has a relative standard deviation of 2… 7% in the upper ng/L range. With a 65-μ polydimethylsiloxane/divinylbenzene-coating on the fiber, the sensitivity of the method can be extended to limits of quantitation in the low ng/L range. However, this fiber, shows an increased susceptibility to matrix effects as observed in the presence of diisopentyl ether, which can only be compensated by using the method of standard addition.  相似文献   

7.
Waste water from ammunition production sites and aqueous samples (ground and surface water) on or near former military sites on which explosives were produced or filled, e.g. into shells, may be contaminated by the original explosives—mainly nitrotoluenes (such as dinitrotoluenes, trinitrotoluene (TNT)) and nitramines (such as hexogen (RDX), octogen (HMX), and tetryl) or hexyl, but also by byproducts and compounds formed by biodegradation of the explosives such as aminonitrotoluenes, chlorinated nitrobenzenes and nitrophenols. These compounds can be extracted from aqueous samples by liquid/liquid extraction (using dichloromethane or toluene) or by solid phase extraction using C-18 adsorbents with high recoveries (usually ≥85%) provided they contain only one amino group. Nitrotoluenes, chlorinated nitrobenzenes and aminonitrotoluenes (nitrotoluidines) may be determined by gas chromatography (GC) using selective detectors such as an electron capture detector (ECD), a nitrogen-phosphorus detector (NPD) or a chemiluminescence detector (thermal energy analyzer, TEA). The use of combined gas chromatography/mass spectrometry (GC/MS) under electron impact conditions is even more specific. Detection limits comparable to an ECD or NPD, however, are only achieved if the mass spectrometer is operated under selected ion monitoring (SIM). Nitrophenols are derivatized after extraction by heptafluorobutyric anhydride or by acetic anhydride where the latter method can be directly applied to the aqueous sample. The nitramine explosives, such as RDX, HMX, and tetryl, hexyl, the nitrate esters, such as nitropenta (PETN) and nitroguanidine as well as picric acid cannot, or only with difficulty, be analyzed by gas chromatography. They may be determined by high performance liquid chromatography (HPLC) with UV-detection. The HPLC analysis can be extended to include also nitrotoluenes and nitroaminotoluenes.  相似文献   

8.
Summary: The application of the UV derivative spectroscopy method to determine aniline and phenol in spiked waste water samples was investigated. Two statistical procedures (modified t-tests) were used to evaluate constant and percentage systematic errors of the method presented. On our conditions, i.e. type of samples, the aniline determination by the 2nd and 4th derivatives was predominantly disturbed but in contrary the phenol concentrations of all samples determined by the 4th and 5th derivatives show no significant bias. The influence of substituted phenols was examined by factor experiments (Plackett-Burman-plan). Generally the higher derivative order brings the better resolving power and in part then the interference is eliminated (p-cresol, hydroquinone).  相似文献   

9.
A reliable and sensitive analytical method for the determination of estrone (E1), 17β-estradiol (E2), and the synthetic hormone 17α-ethinylestradiol (EE2) has been established. Samples are concentrated using automated solid-phase extraction and analysis is performed by liquid chromatography with detection by tandem mass spectrometry. Recoveries of all analytes were between 93% and 107%, and limits of quantification (LOQs) between 0.1 and 0.4 ng/L for purified sewage, and surface, ground, and drinking water, and between 1 and 2 ng/L in case of raw sewage. For the investigation of estrogen release into the environment and its behavior during sewage and surface water treatment, and during ground water recharge, samples from municipal waste water treatment plants (WWTPs), a surface water treatment plant, a bank filtration site, and a ground water enrichment (GWE) pond were analyzed. El was found in the raw waste water with an average concentration of 157 ng/L, whereas E2 and EE2 were found with mean concentrations of only 18 and 9 ng/L, respectively. Sewage treatment by municipal WWTPs affected a removal of EE2 (76%), El (92%), and E2 (94%). In the investigated surface water of Berlin, only E1 could be detected at concentrations around or below 1 ng/L. E2 and EE2 were not present in the Berlin surface water above the LOQ of 0.2 ng/L, respectively. Surface water treatment also leads to a significant removal of E1 (> 80%). In the ground water samples from the GWE site near Lake Tegel, only a few samples contained detectable concentrations of E1. These samples were collected from a shallow monitoring well located very close to the bank of the pond. Even a short distance between the bank and observation wells led to concentrations of El below the LOQ showing the potential of ground water recharge systems for the retention of estrogenic steroids depending on the environmental setting.  相似文献   

10.
A simple and selective solid phase extraction procedure for the trace analysis of iron(III) in water samples has been developed. Sodium dodecyl sulfate coated alumina, modified with polyphenolic compounds (extracted from black tea) was used for the extraction and preconcentration of iron(III) from water samples before determination by flame atomic absorption spectrometry. Due to the complexation reaction between iron(III) and polyphenol compounds, iron(III) was quantitatively extracted on the proposed sorbent and then eluted by 2.0 mL of HCl (1.0 mol/L). The effects of extraction parameters, such as pH and volume of sample solution, amount of polyphenolic compounds, type of eluting agent and the effect of interfering ions on the extraction of iron(III), were investigated. It was found that the proposed method had a good linear range (15.0–100.0 μg/L) and a low detection limit (10.0 μg/L). The procedure was successfully applied for iron determination in drinking water samples.  相似文献   

11.
Structure/reactivity relations are investigated experimentally and theoretically for the microbial degradation of 35 substituted phenols and anilines by adapted mixed cultures of bacteria. From the results one can conclude that the initial attack of the aromatic nucleus has an electrophilic character and is ratelimiting. The results are suitable for predictions of biodegradation rates of organic compounds and facilitate understanding of the mechanism of degradation.  相似文献   

12.
An automated HPLC method is presented which combines on-line ion-pair extraction on small exchangeable RP-C18 precolumns (RP-IPE) with ion-pair chromatography (RP-IPC). Weakly acidic herbicides — carboxylic acids, phenols, and the N-H acidic bentazone — and strong acids, e.g. aromatic sulfonic acids, can be determined simultaneously. Performance data are given. The tetrabutylammonium ion pairs of all investigated compounds are readily transferred from the RP-C18 precolumn to the analytical column by a phosphate buffer/methanol gradient. This is also true for the chlorinated phenoxy acids which, in earlier off-line extraction experiments, could not be desorbed from the RP-C18 material by the lower polar acetone. The RP-IPC is carried out at neutral pH where weakly acidic compounds appear in their stronger UV absorbing dissociated form. Compared to conventional reversed phase chromatography using an acidified eluent, the sensitivity of UV detection is markedly enhanced, especially for the phenol herbicides and bentazone. In addition, phenols can be detected more selectively because they show a second intense absorption band in the wavelength range between 280 nm and 290 nm, where there are only little interferences with the matrix. Due to miniaturization and automation, the online combination IPE/IPC allows a large sample throughput at a lower consumption of solid phase material and organic solvents. Time consuming manual steps are totally missing. The IPE/IPC technique is well suited as a screening method for fate studies of polar micropollutants, e. g. for monitoring the efficiency of different water treatment technologies. An example for balancing an activated carbon filter is presented.  相似文献   

13.
《Marine pollution bulletin》2012,65(12):2834-2838
Polycyclic aromatic hydrocarbons (PAHs) were determined in water samples collected in two streams and a lake located at Niteroi City, Rio de Janeiro State, Brazil between October 2008 and September 2009. Samples were extracted using liquid–liquid extraction and analyzed using high performance liquid chromatography with fluorescence detection. The limits of quantification were sufficiently low to accomplish PAH determination below the maximum concentration levels established by the Brazilian (50 ng/L) and USEPA legislations, with recoveries larger than 81.6%. Phenanthrene, fluoranthene, pyrene and benz[a]anthracene predominated among PAHs. Total concentrations of PAHs were well correlated with rainfall indicating a possible role of runoff to local pollution of water by PAHs and showed a seasonal variation in wet and dry seasons. Our results highlight the contribution of the widespread streams located around Guanabara Bay to the PAH burden found in its waters.  相似文献   

14.
Dispersive liquid–liquid microextraction based on solidification of floating organic droplet (DLLME‐SFO) technique was successfully applied for simultaneous assay of eight polychlorinated biphenyls, two organochlorine, and four pyrethroid pesticides multi‐residue in aqueous samples by using GC‐electron capture detection. The effects of various parameters such as kind of extractant and dispersant and volume of them, extraction time, effect of salt addition, and pH were optimized. As a result, 5.0 µL 1‐dodecanol was chosen as extraction solvent, 600 µL methanol were used as dispersive solvent without salt addition, pH was adjusted to 7. Under the optimized conditions, the limits of detection (LOD) were ranged from 1.4 to 8.3 ng L?1. Satisfactory linear range was observed from 5.0 to 2000 ng L?1 with correlation coefficient better than 0.9909. Good precisions were also acquired with RSD better than 13.6% for all target analytes. The enrichment factors of the method were ranged from 786 to 1427. The method can be successfully applied to simultaneous separation and determination of three class residues in real water samples and good recoveries were obtained ranging from 76 to 130, 73 to 129, and 78 to 130% for tap water, lake water, and industrial waste water, respectively.  相似文献   

15.
Using solid phase extraction followed by HPLC, various pesticides of different chemical structure, thermolabile or polar components included, can be separated and quantitated chromatographically in a single run. Due to longer elution times compared to gas chromatography, only a limited number of components can be determined at the same time. According to our experience, all components relevant for a water catchment area can be covered. With the use of diode-array-detectors the identification of components can be done with sufficient security by comparison of spectra of reference sample and analytical peak. The determination limit is 0.025 μg/L with few exceptions.  相似文献   

16.
Occurrence of Industrial Chemicals (HPS, BPS, and SPS) in Surface Water The paper gives the results of water examinations for different phenylsulfonamides. Random samples taken every month between May 1999 and August 2000 from surface water out of the river Rhine (kilometer 838), the river Ruhr (Mülheim Styrum) and the river Emscher (Oberhausen center) were tested for the corrosion inhibiting agent 6‐[methyl(phenylsulfonyl)amino]‐hexanoic acid (HPS) as well as its metabolites 4‐[methyl‐(phenylsulfonyl)amino]‐butanoic acid (BPS) and sarkosin‐N‐(phenylsulfonyl) (SPS). Furthermore, the sewage plant effluents of two municipal wastewater treatment plants from the rural area were also included in the monitoring program. The analytical method includes solid‐phase extraction (SPE), a derivatization step as well as gas chromatography mass spectrometry (GC‐MS). SPS is regularly found in all investigated surface waters, but only occasionally in the effluents of the two rural sewage plants. The median values for SPS amount to 0.09 μg/L in the river Rhine, 0.60 μg/L in the river Ruhr, and 0.70 μg/L in the river Emscher. BPS can only be found in the river Ruhr (median value: 0.08 μg/L) and in the river Emscher (median value: 0.41 μg/L). HPS was regularly found in a surface water for the first time. This substance can be detected in the Emscher through the whole measurement period. The median value for HPS amounts to 1.78 μg/L. Aditionally, the validation characteristics of an alternative analytical method including solid‐phase microextraction (SPME) is worked out. The fully automated process includes an on‐fiber methylation step and the GC‐MS. The repeatability standard deviation of the process amounts to RSD < 12%. Detection limits between 0.07 and 0.70 μg/L are achieved.  相似文献   

17.
An optimized analysis method based on headspace liquid phase microextraction (HS‐LPME) and gas chromatography coupled with mass spectrometry was proposed for the determination of trihalomethanes (THMs) in drinking water. The response surface method (RSM) was used to optimize the extraction of THMs for analysis by HS‐LPME. The temperature, extraction time and NaCl concentration were found to be important extraction parameters. The coefficient of determination (R2) for the model was 94.97%. A high probability value (P < 0.0001) for the regression indicated that the model had a high level of significance. The optimum conditions were seen to be: temperature 42.0°C, NaCl concentration 0.30 g/mL, and extraction time 28 min. The response variable was the summation of the THMs chromatography peak areas and the reproducibility of this was investigated in five replicate experiments under the optimized conditions. The relative standard deviations (RSD%) of the THMs ranged from 8.0–11.6%. The limits of detection (LODs), based on a signal‐to‐noise ratio (S/N) of three ranged from 0.42–0.78 μg/L, and were lower than the maximum limits for THMs in drinking water established by the WHO.  相似文献   

18.
Formation of Brominated Disinfection By-products after Chlorination of Water from Lake Constance Depending on Treatment Steps and Bromide Concentration The formation of halogenated disinfection by-products (DNP) (trihalomethanes (THM), haloacetic acids (HES), haloacetonitriles (HAN), haloketones (HKE) and chloropicrin (TCNM)) was studied after chlorination (0.5 mg/L) of raw water and drinking water from Lake Constance. The objectives of this study were to investigate the effect of bromide ion on the distribution of DNP-species resulting from chlorination and to draw up a bromide mass-balance. The treatment of water from Lake Constance with ozone decreased the formation of DNP about 35% and of total organic halogens (AOX) about 45%. This decline in DNP-formation is mainly due to the formation of chloroform, dichloro- and trichloroacetic acid. Though there is only a small amount of bromide (6.2 μg/L) in water from Lake Constance, about 32% of THM, 16% of HES, and 30% of HAN contained bromine after chlorination of treated water. The addition of bromide ion (up to 1 mg/L) shifted the DNP-composition to more brominated species. The distribution of the DNP-species depends on the initial molar bromide-to-chlorine ratio. A mathematic model showed the same pattern of DNP-species depending on the initial molar bromide-to-chlorine ratio that was observed experimentally in microstrained raw water and drinking water from Lake Constance. After chlorination of microstrained raw water, 27% of the bromide were incorporated in known DNP, 34% in unknown substances, and about 39% of bromide were not converted to organic bromine. After chlorination of treated water, only 16% of the bromide were incorporated in unknown substances, whereas 34% were found in known DNP. About 50% were found as bromide again. After addition of bromide (up to 25 μg/L) to ozonated and treated water from Lake Constance, between 60 and 72% of the bromide that had reacted after chlorination were found in analyzed low-molecular DNP.  相似文献   

19.
A novel, simple, fast, and efficient ionic liquid‐based dispersive liquid–liquid extraction (IL‐DLLE) has been applied to extract and remove Congo Red (CR; a carcinogenic textile dye) from aqueous solutions. In this methodology a binary solution, containing the extraction solvent (1‐hexyl‐3‐methylimmidazolium bis(trifluormethylsulfonyl) imid) and a suitable disperser solvent, was rapidly injected into the water sample containing CR dye. Therewith, a cloudy solution was formed, and most of the dye molecules were extracted into fine IL droplets and removed from aqueous phase. The effects of pH, type, and amount of IL, initial concentration of the dye, type and volume of the dispersant, and concentrations of salt on the extraction of the dye were studied. Experimental surveys were also accomplished for recovery of the IL by applying a reverse dispersive liquid–liquid extraction using acidic stripping solutions.  相似文献   

20.
Organohalogen compounds are gaining in importance in the control of surface and drinking water due to their unwholesome properties. An accumulation of the organohalogen compounds, occurring mostly at low concentrations, is possible in different ways. The author discusses the possibility and problems of the extractability from waters with the aid of organic solvents. The group parameter EOX that can be determined does not allow any statement concerning components of individual substances, but gives some clues to the state of surface and drinking waters which are mostly anthropogenically polluted. Results of practical examples as well as theoretical considerations indicate the importance of the different distribution coefficients in the solvent/water extraction system. The degree of extraction can be considerably increased by the application of suitable mixtures of solvents. In waters with a known composition, the probably detectable EOX-quantity can be calculated by means of theoretical degrees of extraction.  相似文献   

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