Determination of Chloroethers in Aqueous Samples Using Solid-phase Microextraction

A method for the determination of di- and tetrachlorinated ethers (haloethers) in aqueous samples using solid-phase microextraction (SPME) combined with capillary GC has been developed. Using 100-μm polydimethylsiloxane fibers, the influence of several parameters on the SPME procedure like the exposure time of the fiber in the aqueous sample, the desorption temperature, and the salt content of the sample have been studied. Salt addition has a strong effect on the extraction efficiency of the haloethers investigated. Working with saturated salt solutions, the factor increase of the peak areas was in the range from 5 to 12. These improvements are accompanied by decreased precision and increased equilibration times. The SPME method combined with several detectors (FID, ECD, MS in SIM mode) was evaluated with respect to detection limits, linearities, and precisions. Working with salt addition and FID, detection limits of all compounds investigated were in the range of 0.3 to 1.2 μg/L. Using ECD, the LOD values (limits of detection) were only improved for the tetrachlorinated bis(propyl) ethers (<10 ng/L). Employing mass-spectrometric detection in SIM mode for all chlorinated ethers, detection limits lower than 100 ng/L could be reached. Working with saturated salt solutions, the coefficients of variation were <9% RSD. However, without salt addition, the precision is better than 2.5% RSD for all analytes. Investigations showed that the analysis of the haloethers with SPME is not influenced significantly by the matrix Elbe water. The results of two series of samples demonstrate that SPME-GC-MS allows the sensitive determination of the di- and tetrahalogenated ethers in Elbe river water.     

Occurrence and Distribution of Organic Contaminants in the Aquatic System in Berlin. Part III: Determination of Synthetic Musks in Berlin Surface Water Applying Solid-phase Microextraction (SPME) and Gas Chromatography-Mass Spectrometry (GC-MS)

Polycyclic musks and nitro musks were found as environmental pollutants in screening analyses of 30 representative surface water samples collected from rivers, lakes, and canals in Berlin. These synthetic musks, which are used as fragrances in cosmetics, detergents, and other products, are discharged by the municipal sewage treatment plants into Berlinπs surface waters. In particular, the polycyclic musks 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-(g)-2-benzopyrane (HHCB; Galaxolide®, Abbalide®) and 7-acetyl-1,1,3,4,4,6-hexamethyltetraline (AHTN; Tonalide®, Fixolide®) were found in the receiving surface waters at considerable concentrations up to the μg/L-level. In the Wuhle, a small brook almost totally consisting of sewage effluents, maximum concentrations were 12.5 μg/L for HHCB and 6.8 μg/L for AHTN. Additionally, the polycyclic musk 4-acetyl-1,1-dimethyl-6-tert-butylindane (ADBI; Celestolide®, Crysolide®) and 1-tert-butyl-3,5-dimethyl-2,6-dinitro-4-acetylbenzene (musk ketone) were detected at low concentrations in most of the samples. Two other nitro musks, namely 1,1,3,3,5-pentamethyl-4,6-dinitroindene (musk moskene) and 1-tert-butyl-3,5-dimethyl-2,4,6-trinitrobenzene (musk xylene), were only detected in a single surface water sample. Solid-phase microextraction (SPME) with detection by gas chromatography-mass spectrometry (GC-MS) has proven to be a rapid and reliable tool for the screening of synthetic musks in surface and sewage water samples. Internal calibration with a suitable internal standard enables reproducible quantitation of the analytes down to the low ng/L-level.     

Determination of Organic Phosphonates in Aqueous Samples Using Liquid Chromatography/Particle-beam Mass Spectrometry

Organic phosphonates are widely used, and in general, they are not easily biodegradable. Therefore, our interest was focussed on the development of an analytical method for the trace-level determination of organic phosphonates in water. Our method combines preconcentration of the analytes by evaporating the water sample with the methylation of the phosphonates using diazomethane. Analysis of the totally methylated phosphonates is done by liquid chromatography coupled with mass Spectrometry by the particle-beam interface. The derivatives could be clearly identified by their electron impact mass spectra as well as their chemical ionisation mass spectra. The totally methylated phosphonates can be separated by liquid chromatography using a 125 mm × 4 mm LiChrospher 100 Diol column and a gradient mobile phase containing n-hexane and isopropyl alcohol. After optimizing preconcentration and derivatization procedures as well as all particle-beam and mass spectra conditions, detection limits in the low ppb range were attained.     

Determination of the 13C/12C Isotope Ratio of Organic Compounds for the Biological Degradation of Tetrachloroethene (PCE) and Trichloroethene (TCE)

With the method used here, it was possible to determine the isotope content of both the initial compounds and their metabolites formed due to microbial degradation. The chemical analysis showed that the dominating degradation metabolite for both PCE and TCE degradation was cis-1,2-dichloroethene (cis-1,2-DCE). Apart from this, the formation of TCE, trans-1,2-DCE, 1,1-DCE, chloroethene (VC), ethene and ethane was observed. The isotope analysis showed no measurable fractionation of stable carbon isotopes, for the microbial degradation of PCE and TCE to cis-1,2-DCE. There was a small effect for trans-1,2-DCE and a stronger one for VC as metabolite of TCE.     

Pilot‐Scale Degradation of Organic Contaminants in a Continuous‐flow Reactor by the Helielectro‐Fenton Method

The feasibility of pilot‐scale mineralization of organic pollutants in wastewaters using the Electro‐Fenton® process is demonstrated. The treatment was applied in a continuous‐flow reactor, to solutions of nitrobenzene, 2,4‐D and benzoic acid and to actual wastewaters from a fine chemicals company along with a pulp and paper company. The results showed mineralization yields from 60 to 84% by simply applying the Electro‐Fenton® process. When a subsequent exposure to sunlight was carried out (Helielectro‐Fenton method), this mineralization almost went to completion, except for the effluent from the fine chemicals industry.     

An Improved Gas Chromatographic Method for the Determination of C6–C12 Petroleum Hydrocarbons in Soil Water

In this work, investigations dealing with the determination of hydrocarbons in contaminated soil water are presented. The hydrocarbons under investigation range from low to high volatility compounds. A GC‐FID method was developed that due to its efficiency, routine suitability, relative rapidity, and low cost is suitable for the analysis of complex chemical mixtures of highly volatile hydrocarbons (with boiling points between 69 and 190°C). The standard used was a gasoline mixture with boiling points ranging from 100 to 190°C. For this standard, no supplementary preparation is needed and it is suitable for the whole range of hydrocarbons under investigation. The determination of the hydrocarbon content of the samples was performed applying univariate and multivariate statistical analysis to the experimental data. In the characterization of a contamination with highly volatile hydrocarbons of soil water originating from different depth layers from the chemistry location Leuna (Sachsen‐Anhalt, Germany), the advantages of a multivariate method are demonstrated in exemplary manner.     

Development of Dispersive Liquid–Liquid Microextraction Based on Solidification of Floating Organic Drop for the Determination of Trace Lead in Water

A new method for determining lead (Pb) content was developed by dispersive liquid–liquid microextraction based on the solidification of floating organic droplets followed by flame atomic absorption spectrometry. Under optimum conditions, the calibration graph was linear within the Pb content range of 8.43–400 µg L^?1 with a detection limit of 2.53 µg L^?1. The relative standard deviation for 10 replicate measurements of 20 and 400 µg L^?1 of Pb were 3.41 and 2.78%, respectively. The proposed method was assessed through the analysis of certified reference water and recovery experiments.     

Development of an Analytical Method for the Determination of Trace Lead in Lake Water Samples by Flame Atomic Absorption Spectrophotometry after Vortex Assisted-Stearic Acid Coated Magnetic Nanoparticle Based Extraction

In the present study, a method is proposed for the determination of lead at trace levels by slotted quartz tube-flame atomic absorption spectrophotometry (SQT-FAAS) after preconcentration with stearic acid coated magnetic nanoparticle-based dispersive solid phase extraction (SA-MNP-DSPE). The slotted quartz tube (SQT) is used to enhance the analyte atom residence time in the light path. Stearic acid coated magnetic iron oxide (Fe₃O₄) nanoparticles, which can be easily collected with an external magnet, are used as adsorbent in the extraction process. The limit of detection (LOD) and the limit of quantitation (LOQ) values of the proposed method are obtained as 0.90 and 2.9 µg L⁻¹, respectively. The method allows high repeatability in a wide linear range between 5.0 and 250 µg L⁻¹, and the relative standard deviation for six replicates is 5.8%. The detection power is enhanced by about 77-fold compared to the regular flame atomic absorption spectrophotometry (FAAS) system. The method is validated by recovery experiments to four different lake water samples. After the spiking tests, good recovery results are calculated between 97% and 106%. These results show that lead can be detected at low levels in lake water samples with high sensitivity, accuracy, and precision.