Electroosmotic flow patterning using microfluidic delay loops.

A theoretical and experimental investigation of alternating electroosmotic flow patterns by means of specially designed delay loops is presented. Using elementary methods of compact network modeling and detailed FEM simulations the flow behavior and, in particular, the rearrangement of sample plugs is modeled. The proposed designs rely on flow splitting in combination with electroosmotic delay loops leading to a runtime difference or phase shift between two sub-streams. Due to this phase shift, a new fluid interface is generated at the merging point. The approach is experimentally validated by injection of a Rhodamine 6G solution into an aqueous sodium tetraborate buffer.

Solid-phase micro extraction (SPME) and headspace derivatization of clenbuterol followed by GC-FID and GC-SIMMS quantification.

Solid-phase micro extraction (SPME) and on-fiber derivatization followed by Gas Chromatography coupled with Flame Ionization Detection (GC-FID) or Selected Ion Monitoring Mass Spectrometry (GC-SIMMS) allows for simple yet sensitive quantification for the hexamethyldisilazane derivative of the beta-agonist clenbuterol. Using an 85- micro m polyacrylate fiber, the analysis method is optimized with respect to extraction time, derivatization time and temperature, and solution pH. In addition, the use of a rapid temperature ramping injection port allows for optimization of fiber desorption conditions. Under optimal conditions, the limits of detection for the hexamethyldisilazane derivative of clenbuterol are 1.1 ppb by FID and 0.20 ppb by SIMMS.

Carbon-based quantitation of pyrethrins by supercritical-fluid chromatography.

All six insecticide active ingredients in pyrethrum extract were quantified by supercritical fluid chromatography and carbon calibration. Allethrin is a suitable reference compound for carbon calibration and pyrethrins calibrations. Carbon quantification in SFC is also applied to pyrethroids (phenothrin, permethrin, cypermethrin, fenvalerate and deltamethrin) and alkanes. Halogen substitution on pyrethroids requires halogens on the reference calibration compound. The method was applied to commercial extracts.

Remediation of a nonachloro biphenyl congener with zero-valent iron in subcritical water.

Dechlorination of a nonachloro biphenyl congener with zero-valent iron in water under high temperature and pressure was investigated over time. Temperature has the main influence on the speed of dechlorination. Determination of polychlorinated biphenyls (PCBs) according to the grade of chlorination was performed by gas chromatography with mass selective detection in single ion monitoring mode. Dechlorination results in a variety of lower chlorinated biphenyls. The level of chlorination decreases with time. The amount of PCB molecules decreases to one-third within 90 min at 250 degrees C and 100 atm. However, no increase of biphenyl could be detected over time. A first-order kinetic model fitted the data obtained.

Extraction of polychlorinated biphenyl with supercritical carbon dioxide, sulfur hexafluoride and subcritical water.

In the extraction of spiked PCB from soil, three extracting fluids were investigated: supercritical carbon dioxide (CO2), supercritical sulfur hexafluoride (SF6) and subcritical water. Among the tested fluids SF6 appeared to be appropriate especially for the extraction of low polar PCB. CO2 and water were found to be suitable for the quantitative extraction of all PCB. Water was judged as the best because of its low price, good availability and environmental safety.

Extraction of PCDD/PCDF from soil with supercritical CO2: optimization by a three-level factorial design approach.

Two factors (pressure and temperature) varied over three levels were optimized for the extraction of PCDD/F from native contaminated soil with toluene-modified supercritical carbon dioxide. Temperature had a strong positive effect on the recovery. The most efficient extraction was achieved at 120 degrees C. This is in contrast to the influence of the temperature on the extraction of HCH, where a higher recovery is obtained at 60 degrees C than at 150 degrees C. The optimized conditions found for this soil were applied to the analysis of a BCR (European Commission) reference material prepared from contaminated industrial soil. The results are in good agreement with those of an interlaboratory study.

Copper-complexation index as a polarographic summation parameter for the determination of chelating agents in water.

Polarography of the copper(II)-complexes of chelating agents is shown to be a suitable basis for a summation parameter for the total concentration of these chemicals in water (expressed as the copper-complexation index). Using 12 chelating agents (ATMP, BAED, CDTA, DTPA, DTPMP, EDTA, EDTMP, EDTP, EGTA, HEDP, NTA, PBTC) all listed in DIN 38409-H26 and DIN 38413-P5 a satisfactory reproducibility of the method used was obtained. In addition several commercial tensides, detergents in washing and deliming products were investigated.

Temporal variability of organic micropollutants in suspended particulate matter of the River Elbe at Hamburg and the River Mulde at Dessau, Germany.

The compound classes of n-alkanes, polycyclic aromatic hydrocarbons (PAHs), and a number of chlorinated hydrocarbons (CHs) in the River Elbe and its tributary Mulde were investigated on the basis of monthly mixed samples of suspended particulate matter (SPM). Covering the period from September 1994 to August 1995, samples from the River Elbe were taken at Hamburg, those from the River Mulde at Dessau. The samples were extracted by supercritical fluid extraction (SFE). Analysis of all substance groups were performed by highperformance liquid chromatography (HPLC), followed by gas chromatography with mass spectrometric detection (GC/MSD). As a statistical approach for the interpretation of data, hierarchical cluster analysis of the individual compound classes were performed to determine differences or similarities between the sampling sites Hamburg and Dessau to find spatial and seasonal concentration patterns. These analysis showed that, with a high significance, the concentration patterns of n-alkanes, PAHs, and CHs were sampling site-specific in both the Elbe and Mulde throughout the entire sampling period. In all cases, clustering of mostly consecutive months indicated continuous, slow changes of input, which moreover showed a constancy with respect to annual cycles. Correlation analysis of pollutant loads with different hydrographic parameters showed a number of linear dependencies of the contaminants with temperature, SPM content, and water discharge. Annual fluxes of particle-bound pollutants were calculated for each sampling site, taking into account the average monthly SPM levels and the water discharge. The particle-bound pollutant loads for the River Elbe at Hamburg were estimated to 13.4 t/a n-alkanes, 4.1 t/a PAHs, and 175. 8 kg/a CHs. The pollutant loads for the River Mulde at Dessau amounted 0.55 t/a n-alkanes, 0.14 t/a PAHs, and 15.5 kg/a CHs during the monitoring period. The input of n-alkanes originated from different sources. The n-alkane pattern of samples of the River Elbe showed a predominance of odd-numbered compounds in the range of C-20 and C-30 originating from terrestrial plants and, depending on the season, high concentrations of C-15 and C-17 due to aquatic organisms. Only a small proportion of n-alkane input originated from petroleum sources. Samples from the River Mulde showed high amounts of the n-alkanes C-12 to C-15, indicating the input of light oil throughout the entire sampling period, constituting approximately 25% of the total n-alkane concentration. PAHs, which are considered combustion products, were widely distributed in all samples. Although the major inputs of PAHs were probably combustion sources and urban runoff, unusually high concentrations were found for some PAHs, which can be explained by point sources. A comparison of the standardized PAH patterns in samples from both stations clearly showed that higher fused ring systems, which mainly originate from combustion processes (four- to six-ring systems), had considerably higher relative concentrations in SPM from the Elbe than from the Mulde, where higher relative concentrations of the two- and three-ring systems were measured. This confirms findings that petroleum input was higher in the Mulde than in the Elbe. Concentrations of chlorinated hydrocarbons in SPM samples from the river Mulde had comparatively high levels. The largest differences were found for p,p'-DDT and its metabolites p,p'-DDD and p,p'-DDE. On average, concentrations of p,p'-DDT, p,p'-DDD, and p,p'-DDE in the Mulde were about 10, 15, and 25 times higher, respectively, than in the Elbe. Concentrations of HCB, which in the samples from Hamburg had the highest concentrations of all CHs, were found to be higher by about a factor of 3 in the Mulde River. The PCB levels in samples from the Mulde and Elbe were about equal, although there were differences in the pattern of PCB congeners.

Distribution of platinum group elements (Pt, Pd, Rh) in environmental and clinical matrices: Composition, analytical techniques and scientific outlook: Status report.

Trace concentrations of the platinum group elements (PGE; here: Pt, Pd and Rh) play an important role in environmental analysis and assessment. Their importance is based on 1. their increasing use as active compartments in automobile exhaust catalysts, 2. their use as cancer anti-tumor agents in medicine. Due to their allergenic and cytotoxic potential, it is necessary to improve selectivity and sensitivity during analytical investigation of matrices like soil, grass, urine or blood. This paper summarizes the present knowledge of PGE in the fields of analytical chemistry, automobile emission rates, bioavailability, toxicology and medicine.

Determination of Chlorinated Hydrocarbons in Marine Sediments at the Part-per-Trillion Level with Supercritical Fluid Extraction.

An off-line supercritical fluid extraction method has been developed for the determination of polychlorinated biphenyls and organochlorine pesticides at the part-per-trillion level in marine sediments. Four different extraction conditions were evaluated: pure carbon dioxide at 60 °C/220 atm and 100 °C/350 atm; addition of methanol prior to the static extraction at 80 °C/350 atm; addition of methanol prior to the static extraction step and continuously during the dynamic extraction step at 80 °C/350 atm. Only the latter condition gave extraction recoveries that were comparable and for some compounds higher than Soxhlet recoveries. The significance of differences between the two extraction methodes was determined in an F- and t-test. The method was validated by analysis of a reference material from an international intercomparison exercise.

Optimization of SFE for the Determination of Chlorinated Hydrocarbons at the Part-per-Trillion Level.

The applicability of SFE for trace analysis was expanded by an intensive cleaning procedure of the SFE equipment and development of an adsorbing device for commercial carbon dioxide. For a selection of chlorinated hydrocarbons, the limit of detection was reduced to ≤20 pg/g of solid matrix. The procedure can be transferred to other analytical SF delivery systems for off- and on-line SFE, and also to an SFC apparatus. Also, the blank value for the analysis of nonchlorinated aliphatic and aromatic compounds was improved significantly. The purity of carbon dioxide is no longer the limiting factor for trace analysis with SFE.

Comparison of ASE and SFE with Soxhlet, Sonication, and Methanolic Saponification Extractions for the Determination of Organic Micropollutants in Marine Particulate Matter.

The methods of accelerated solvent extraction (ASE) and supercritical fluid extraction (SFE) of polycyclic aromatic hydrocarbons (PAHs), aliphatic hydrocarbons, and chlorinated hydrocarbons from marine samples were investigated. The results of extractions of a certified sediment and four samples of suspended particulate matter (SPM) were compared to classical Soxhlet (SOX), ultrasonication (USE), and methanolic saponification extraction (MSE) methods. The recovery data, including precision and systematic deviations of each method, were evaluated statistically. It was found that recoveries and precision of ASE and SFE compared well with the other methods investigated. Using SFE, the average recoveries of PAHs in three different samples ranged from 96 to 105%, for ASE the recoveries were in the range of 97-108% compared to the reference methods. Compared to the certified values of sediment HS-6, the average recoveries of SFE and ASE were 87 and 88%, most compounds being within the limits of confidence. Also, for alkanes the average recoveries by SFE and ASE were equal to the results obtained by SOX, USE, and MSE. In the case of SFE, the recoveries were in the range 93-115%, and ASE achieved recoveries of 94-107% as compared to the other methods. For ASE and SFE, the influence of water on the extraction efficiency was examined. While the natural water content of the SPM sample (56 wt %) led to insufficient recoveries in ASE and SFE, quantitative extractions were achieved in SFE after addition of anhydrous sodium sulfate to the sample. Finally, ASE was applied to SPM-loaded filter candles whereby a mixture of n-hexane/acetone as extraction solvent allowed the simultaneous determination of PAHs, alkanes, and chlorinated hydrocarbons.

High-performance liquid chromatographic determination of primary amines in aqueous solutions after extraction and derivatization with 2,2-diphenyl-1-oxa-3-oxonia-2-boratanaphthalene (DOOB).

Aqueous solutions of tryptamine, tyramine and ethanolamine are extracted and derivatizated to azomethine chelates using a solution of DOOB in diethyl ether. The extraction takes about 2 h. Diisopropyl ether and toluol have also been tested as extractants. The separation of the azomethine chelates is realized by a gradient program on a Si 60 column using a mixture of n-heptane/tert-butyl methyl ether. UV detection is carried out at 280 nm. The concentration of these three amines has been determined in a Chianti wine sample.

High-performance liquid chromatographic investigations on the time-dependent reaction of cis-Pt(NH3)2Cl2, Pt(en)Cl2 and Pt(pn)Cl2 with RNA fragments.

The reaction of three platinum compounds, Pt(NH3)2Cl2, Pt(en)Cl2 and Pt(pn)Cl2 with nucleic acid fragments (Ade, Gua; GpG, GpA and ApA), both reactants (1:1, 1 X 10(-2) M; 1 X 10(-3) M) being dissolved in water, has been studied. UV measurements have been used to characterize the products. Kinetics and adduct formation in the nucleoside-Pt compound system were studied by reversed-phase high-performance liquid chromatography [gradient 0-30% methanol in 30 min, ammonium acetate buffer (0.1 M) at pH 4.25] at fixed intervals of time and the product formation was examined by measuring the peak heights. After 10 h, the reaction was complete for guanosine and showed a steady state for adenosine. The increasing lipophilicity in the sequence of the platinum compounds resulted in a shift to longer retention times.