Gaschromatographische Bestimmung von polychlorierten Biphenylen in Wasser nach Headspace-Festphasenmikroextraktion

Gas-chromatographic Determination of Polychlorinated Biphenyls in Water after Headspace Solid-phase Microextraction Headspace-analytical techniques are usually applied to the determination of easily volatile substances in water, whereas semivolatiles are generally isolated by liquid-liquid or solid-phase extraction. In the present paper, a method is presented for isolating high boiling polychlorinated biphenyls (PCB) using headspace solid-phase microextraction at elevated temperature. In spite of their low vapor pressure, the analytes are adsorbed very efficiently on a poly-dimethylsiloxane-coated fiber. Thus, in combination with GC/ECD, a very simple and sensitive solventless determination of PCB is accomplished. Using the simplest possible standard conditions, limits of determination in the lowest nanogram-per-liter range are achieved. Further increased sensitivity down to the ppq (parts per quadrillion) range is possible by stirring and increasing the sample volume and adsorption time. Moderate matrix effects have been observed in some surface and groundwaters.     

Sorption and Chemical Reactions of PAHs with Dissolved Humic Substances and Related Model Polymers

Sorption coefficients measured for PAHs on dissolved humic substances by SPME and FQT were found to be inevitably different and method‐dependent – SPME provides activity‐based and FQT concentration‐based sorption coefficients. Poly(acrylic acid) esters as well‐defined model polymers were used in sorption experiments, leading to the conclusion that short aliphatic chains are more effective in binding PAHs than aromatic moieties. FQT was inappropriate to measure sorption coefficients for the interaction of pyrene with poly(acrylic acid) esters but the experiments revealed a characteristic shift in the fluorescence spectrum. Using pyrene as a probe for the molecular environment in the sorbed state, the observed spectral shift indicated a highly hydrophobic microenvironment. The empirical relationships between lg K_DOC and lg K_OW were generalized on the basis of a modified Flory‐Huggins concept. Introducing only one sorbent‐specific parameter, the solubility parameter δ_DOM, the calculation of sorption coefficients became possible for a wide range of HOCs using fundamental data readily available from the literature. Long‐term experiments showed that reactive PAHs (such as acenaphthylene and 9‐methylanthracene) are able to react with HAs under strictly abiotic and anoxic conditions, whereas less reactive PAHs (such as naphthalene and dihydroanthracene) do not form bound residues. The HA reveals two functions in the interaction, behaving as a reaction partner and as a protecting ligand.     

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.     

Occurrence and Distribution of Organic Contaminants in the Aquatic System in Berlin.Part II: Substituted Phenols in Berlin Surface Water

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.     

Speciation and Determination of Inorganic Mercury and Methylmercury by Headspace Single Drop Microextraction and Electrothermal Atomic Absorption Spectrometry in Water and Fish

In this study, headspace single drop microextraction (HS‐SDME) method in combination with electrothermal atomic absorption spectrometry (ETAAS) method was developed and validated for the speciation and determination of inorganic mercury (iHg) and methylmercury (MeHg). MeHg and iHg species were reduced to volatile methylmercury hydride (CH₃HgH) and elemental mercury, respectively, in the presence of NaBH₄ and trapped onto a drop of acceptor phase in the tip of a microsyringe. Thiourea and ammonium pyrrolydinedithiocarbamate (APDC) were tested as the acceptor phase. The experimental parameters of the method such as microextraction time, temperature, NaBH₄ concentration, acceptor phase concentration, and pH of the medium were investigated to obtain distinctive conditions for mercury species. Possible interference effects have also been investigated. In order to validation of the method, analytical figures of merits such as accuracy, precision, limit of detection (LOD), limit of quantitation (LOQ), and linear working range have been evaluated. Accuracy of the method has been verified by analyzing certified reference materials (BCR 453 Tuna fish) and spiked samples. The proposed method was applied for the speciation and determination of mercury species in water and fish samples. Mercury species (MeHg and iHg) have been determined in the real samples with a relative error less than 10%.     

Toxicity-directed Fractionation of Tannery Wastewater Using Solid-phase Extraction and Luminescence Inhibition in Microtiter Plates

A four-step solid-phase extraction (SPE) method is presented for toxicity-directed fractionation of industrial wastewater. This fractionation procedure serves as a key step for identifying unknown organic toxicants in complex samples. Toxicity was determined as luminescence inhibition of Vibrio fischeri using microtiter plates. This method was compared to standard tests in glass cuvettes using both 37 standard chemicals and 24 wastewater fractions with EC₅₀ values covering five orders of magnitude. Results of both methods correlated well. 22 tannery wastewater samples were sequentially extracted using C₁₈e and polystyrene-divinylbenzene phases in combination with pH-changes. Final solid-phase filtrates showed low inhibition, so toxicity of inorganics could be neglected. Using 1/EC₅₀ values, the SPE eluates showed clearly different toxicity patterns. Even in eluates of the fourth extraction step, high toxic effects could be observed. In several cases, luminescence inhibition was increasing at the anaerobic treatment step compared to the corresponding untreated samples. After aerobic treatment, toxicity of most wastewater fractions was greatly diminished. HPLC/DAD analyses of the wastewater fractions showed a fair separation concerning compound polarity. However, the samples were still too complex to identify single compounds responsible for the detected toxicity. Therefore, a further clean-up step accompanied with toxicity testing is needed.     

Development of a SPME-GC Method for the Determination of Organic Compounds in Wastewater

A manual SPME method is presented for the analysis of organic compounds in industrial wastewater. 24 compounds commonly found in the wastewater of a chemical plant in northern Germany have been selected as reference compounds. Precision, linearity, and detection limits have been determined. Moreover, the effect of methanol content, pH value, salt content, and an excess of compounds on the extraction process have been studied. Several compounds have been investigated for their applicability as internal standards to quantify the compounds of interest. Since the method will later be transferred to a fully automated SPME-GC system, which will be operated directly on-site at an industrial wastewater purification plant, special attention has been paid to the analysis of real wastewater samples. In this context, the fibre stability has been studied by performing 53 extraction/desorption cycles from one wastewater sample. Neither a decrease in fibre performance nor in precision has been observed indicating that the proposed method is suitable for the analysis of real wastewater.     

Synthesis and characterization of peptides after high-energy impact on the icy matrix: Preliminary step for further UV-induced formation

In the interstellar medium, the most probable source of organic molecules could be non-equilibrium processes driven by photons, cosmic rays, shock waves and solid bodies’ collisions. The dense cold phase of ISM host icy dust grains—important chemical catalyst during its life cycle. Such particles consist of mineral core composed by silicate or olivine admixed with metal sulfides and oxides, with the water-icy envelope containing organic molecules. Organic molecules in the ISM evolve and become later incorporated in solar system material (comets and meteorites).The formation of polypeptides from single amino acids was traced in simulation experiments representing the inner structure of icy dust grains. Experimental chamber was irradiated at subzero temperatures at the dosage of 2.54 kRad/min. Solid frozen solutions of Gly and Phe were taken as the experimental samples inserted into the metal tube kept at subzero temperatures in the presence of liquid nitrogen. Formation of di- and tri-peptides was demonstrated after applying mass-spectrometry and high performance liquid chromatography (HPLC) techniques.Having polypeptides within the icy matrix, dust grains with ice mantles are transported to warm, dense and active protostellar regions, where ultraviolet irradiation may become important and alter the grain composition. Furthermore UVC radiation may contribute to the formation of additional amounts of polypeptides, since short-wave photons are totally adsorbed by a thin outer layer. This presumption coincides with our previous investigations concerning UV impact on prebiotic formation of the main biological molecules. Combination of two irradiation types in different stages of interstellar flight could compensate the effects of low reagents concentration and temperature. Since the primordial Earth had no atmosphere, the natural carriers could get freely onto its surface and thus raise the concentration of organic molecules.     

Application of AMD to the Determination of Crop Protection Agents in Drinking Water. Part IV: Fundamentals of a Confirmatory Test

A method is described for the determination of fifteen active ingredients of plant protecting products in ground-, raw, and drinking water. After extraction and enrichment of the pesticides from the water sample with solid-phase extraction, the extract is fractionated on silica-coated TLC plates, first in a so-called screening gradient by AMD (automated multiple development). The detection of the pesticides is performed by UV multidetection. Positive results from the first separation are confirmed by a second separation on silica in an AMD gradient of distinctly different selectivity, compared to the first separation. Following this strategy, it is possible to distinguish nearly all nonvolatile, from water extractable, active ingredients of plant protecting products in the market. UV spectra are taken for further confirmation of positive results. In most cases, this is possible even at the limit of determination. All chromatograms and spectra shown are raw data, resulting from the confirmatory test DIN 38407 part 11, in the laboratory of one participant*). The method is standardized in the meantime as DIN V 38407-11.     

Bestimmung von Pflanzenbehandlungsmitteln in Wasser durch Online-Fest-Flüssig-Extraktion und HPLC-DAD

Determination of Pesticides in Water by On-line Solid-phase Extraction and HPLC-DAD This paper describes an HPLC on-line procedure for the determination of 29 relevant pesticides in water by diode-array detection using a compact HPLC-system with integrated column-switching. The sample – 5 mL – is injected with a large volume injection system on a precolumn cartridge (RP-C18). Enriched compounds are eluted in frontflush mode by columnswitching to a microbore column and separated with a gradient water/acetonitrile. During desorption the precolumn cartridge is heated at 80°C resulting in a comparable efficiency to the separation with direct injection. The procedure is fully automated for continuous monitoring of drinking-, ground-, and surface water with low contamination levels. Sample preparation is limited to a filtration step with an anion-exchange membrane filter to reduce natural contaminations e.g. humic acids simultaneously. For a concentration of 50 ng/L, the signal to noise ratio varies from 3:1 (Ethidimuron) up to 25:1 (Chloridazon). The standard deviations compare to the standardized HPLC-method DIN EN ISO 11369; the recovery rates are 100% and reproducible. The method was successfully tested on ruggedness with several sequences from a monitoring program. The precolumn cartridge needs replacement after 100 sample injections. Finally, this method was coupled with a benchtop mass-spectrometer (electrospray mode) without changing the chromatographic conditions. With selected ion monitoring (SIM) selectivity and detection sensitivity could be improved considerably compared to DAD-detection.