Arylesters of alkylsulfonic acids in sediments Part III of organic compounds as contaminants of the Elbe River and its tributaries

Sediments from the Elbe River and from its major tributaries are shown to be contaminated with arylesters of alkylsulfonic acids. Here we report on the structure elucidation and quantification of aryl esters of alkylsulfonic acids. Chromatographic separation and mass spectrometric properties are discussed. Congener-specific analyses revealed a highly similar pattern throughout the area investigated. Alkylsulfonic acid phenylesters were present at almost all sampling locations. Amounts ranged from 33 000 μg/kg near the industrial region of Bitterfeld to 15 μg/kg in wadden sea sediments. Concentrations of alkylsulfonic acid cresylesters were between 10–40% of the phenylesters, and fell below the detection limit only in the Elbe estuary. The presence of aryl esters of alkylsulfonic acids in all sediment samples analyzed indicates a widespread distribution of these compounds in the environment. Previous literature described these compounds erroneously as phenoxyalkanes. Received: 5 August 1997 / Accepted: 21 August 1997     

Organic compounds as contaminants of the Elbe River and its tributaries

GC/MS non target screening has been applied to water samples taken during 1992–1994 from the Elbe river and its tributaries Mulde, Saale, Weiße Elster, Schwarze Elster, and Havel. Based on full scan electron impact mass spectra and supplemented by extensive use of chemical ionisation and high resolution data as well as by synthetic reference compounds, several new classes of compounds, whose possible environmental effects are yet unknown at present, have been identified. Tetrachlorinated bis-(propyl)ethers are new among the most prominent contaminants throughout the Elbe river. The confluence with the Mulde river adds a variety of compounds, related to the chemistry of chloro- and nitroaromatics, azo dyes, benzanilides, carbamates, thiophosphates, and pesticides. The combined load of the Weiße Elster and Saale rivers carries oligoformals, oxathiamacrocycles, and dichloro- and trichloro-bis-(propyl)ethers, whereas chloropropylphosphates are introduced via the Schwarze Elster. The majority of these compounds, originating from sources at the tributaries, are still present at the mouth of the Elbe river. In addition to specific industrial emissions, a variety of more generally observed organic compounds like long chain aliphatics, sterols, phenylalkanes, and plasticizers as well as ubiquitous environmental trace pollutants like polycyclic aromatic hydrocarbons, chlorobenzenes, and hexachlorocyclohexane isomers have been encountered throughout the Elbe river drainage system.Part I: S. Franke, S. Hildebrandt, W. Francke, H. Reincks (1995) Naturwissenschaften 82: 80–83     

Analytical aspects of some organic acids Part III

Summary m-Phenylenedioxydiacetic acid gives a white precipitate with thorium even in the absence of an electrolyte which is quantitative up toph 4. Be²⁺, Mg²⁺, Ca²⁺, Zn²⁺, Pb²⁺ and Mn²⁺ ions are removed by single precipitation and Al³⁺, UO₂ ²⁺ and trivalent cerite earth ions are removed by double precipitation. Sn²⁺, Sn⁴⁺ and Cr³⁺ ions interfere.Part II: See. Z. analyt. Chem.165, 343 (1959).     

Determination of organic sulphur compounds in sediments of the river Elbe using gas chromatography with flame photometric detection

Sediment samples from different reference sites representing typical situations on the river Elbe were analyzed for organo-sulphur compounds (OSC). Gas chromatography with sulphur specific flame-photometric detection was used for the identification and quantification of individual OSC. Chromatographic retention data for 42 standard heterocycles were determined and compared with the composition of sediment extracts. An extraction scheme used for the OSC determination is described. Dibenzothiophene (DBT), its alkylated homologues, phenanthro[4,5-bcd]thiophene, benzo[b]naphtho[2,1-d]thiophene and in some cases still unidentified compounds were the predominant OSC. Depending on sampling site and date the qualitative composition of sulphur heterocycles detected by the described method varied, and the total concentrations of all OSC ranged from 0.3 to 21 mg/kg.     

Isotopic characteristics of the Garonne River and its tributaries

The Garonne is the largest river in the south‐west of France, and its drainage basin stretches between the Pyrénées and the Massif Central mountains. Until now, no water stable isotope study has been performed on the whole Garonne river basin which is composed of different geological substrata, and where the water resources are limited during the dry summer period. This study focuses on the Garonne river and its tributaries from the Pyrénées foothill upstream to its confluence with the Lot River downstream. The aim of the study is to determine the origins of the surface waters using their chemical and stable isotopic compositions (¹⁸O, D and ¹³C), to better understand their circulation within the drainage basin and to assess the anthropogenic influences. The Garonne displays a specific ¹⁸O seasonal effect, and keeps its Pyrénean characteristics until its confluence with the Tarn River. The difference in the dissolved inorganic carbon (DIC) comes mainly from the change in lithology between the Pyrénées and the Massif Central mountains. Agriculture activity is only detected in the small tributaries. Copyright © 2009 John Wiley & Sons, Ltd.     

Ultra-high-performance supercritical fluid chromatography-mass spectrometry for the analysis of organic contaminants in sediments

A nontarget screening method was developed based on D-optimal designs for ultra-high performance supercritical fluid chromatography with positive and negative electrospray ionization mode mass spectrometry. A mixture of organic contaminants such as pesticides, steroids, surfactants, phenolic and fatty acids, and polycyclic aromatic hydrocarbon derivatives, was used for the optimization. An aprotic mixture of dichloromethane and acetone [3:1] performed overall best as the injection solvent. The highest peak capacities (n) were accomplished at the shallowest gradient (1%B/min), ammonium formate (n = 378 in negative ionization mode), or ammonium acetate (n = 327 in positive ionization mode) in methanol as the modifier. Capillary voltage, make-up solvent flow rate, water, and additive concentration were the most significant factors for improving peak intensity: higher peak intensities were obtained at lower additive concentrations (5mM ammonium formate), and with 5% water in positive ionization mode. Conversely, water had detrimental effects in negative ionization mode. The optimized method was used to quantify organic contaminants in 17 freshwater sediment samples from Copenhagen, Denmark. Out of 50 monitored contaminants, 35 were detected in at least one sample. Further, the method has a potential for target and nontarget screening analysis of organic contaminants in solid matrices.     

Mass spectrometric identification of polychlorinated dibenzothiophenes (PCDBTs) in surface sediments of the River Elbe

HRGC/MS was applied to six sediment samples from River Elbe for the determination of polychlorinated dibenzothiophenes (PCDBTs). Among the studied tri-, tetra- and octa-chlorinated isomers, trichlorinated species were found to be the dominating ones. The estimated concentration levels of the compounds were in the range of approximately 0.02–2 μg/kg dry weight for trichlorinated and 0.1–0.3 μg/kg for octachlorinated species. Tetrachlorinated dibenzothiophenes could not be detected.     

Mass spectrometric identification of polychlorinated dibenzothiophenes (PCDBTs) in surface sediments of the River Elbe

HRGC/MS was applied to six sediment samples from River Elbe for the determination of polychlorinated dibenzothiophenes (PCDBTs). Among the studied tri-, tetra- and octa-chlorinated isomers, trichlorinated species were found to be the dominating ones. The estimated concentration levels of the compounds were in the range of approximately 0.02–2 μg/kg dry weight for trichlorinated and 0.1–0.3 μg/kg for octachlorinated species. Tetrachlorinated dibenzothiophenes could not be detected. Received: 7 October 1997 / Revised: 4 February 1998 / Accepted: 9 February 1998     

Analysis of industrial contaminants in indoor air: Part 1. Volatile organic compounds,carbonyl compounds,polycyclic aromatic hydrocarbons and polychlorinated biphenyls

This article reviews recent literature on the analysis of industrial contaminants in indoor air in the framework of the REACH project, which is mainly intended to improve protection of human health and the environment from the risks of more than 34 millions of chemical substances. Industrial pollutants that can be found in indoor air may be of very different types and origin, belonging to the volatile organic compounds (VOCs) and semivolatile organic compounds (SVOCs) categories. Several compounds have been classified into the priority organic pollutants (POPs) class such as polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins and furans (PCDD/PCDFs) and related polychlorinated compounds, and polycyclic aromatic hydrocarbons (PAHs). Many of these compounds are partially associated to the air gas phase, but also to the suspended particulate matter. Furthermore, settled dust can act as a concentrator for the less volatile pollutants and has become a matrix of great concern for indoors contamination. Main literature considered in this review are papers from the last 10 years reporting analytical developments and applications regarding VOCs, aldehydes and other carbonyls, PCBs, PCDDs, PCDFs, and PAHs in the indoor environment. Sample collection and pretreatment, analyte extraction, clean-up procedures, determination techniques, performance results, as well as compound concentrations in indoor samples, are summarized and discussed. Emergent contaminants and pesticides related to the industrial development that can be found in indoor air are reviewed in a second part in this volume.     

Reaction of organic sulfur compounds with superoxide anion—III : Oxidation of organic sulfur compounds to sulf1nic and sulfonic acids

Organic sulfur compounds such as disulfide, thiolsulfinate, thiolsulfonate, thiol, sodium thiolate, and sodium sultinale were readily oxidized to both sulfinic and sulfonic acids with superoxide anion generated from potassium superoxide and 18-crown-6-ether under mild conditions. However, both sulfide and sulfoxide did not react with superoxide anion, O₂^-. Although thiol was easily oxidized to disulfide with O₂^? at room temperature, it was oxidized further with O₂^? at 60° to the corresponding sulfinic and sulfonic acids. Symmetrical disulfide was obtained in the reaction of unsymmetrical thiolsulfinate or thiolsulfonate along with both sulfinic and sulfonic acids. Most reactive was thiolsulfinate which reacted at lower temperature ranging between ?40 and 0° to afford the products within 30 min. Relative reactivities fall in the following order: thiolsulfinate > thiolsulfonate > disulfide ? sodium thiolate ? sodium sulfinate. Polar solvents such as pyridine and acetonitrile were more effective than such a less polar solvent as benzene in the oxidation of the substrate, and increased amount of the crown ether shortened the reaction time. Nucleophilic attack of O₂^? and electron transfer processes are believed to be involved in these oxidations.     

Organometallic species of the elements tin, mercury and lead in sediments of the longitudinal profile of the River Elbe

In 1992, for the first time, a whole longitudinal sediment profile of the River Elbe from the Czech Republic to the North Sea has been sampled within the framework of the project Registration and assessment of harmful substances in the River Elbe: Heavy metals and heavy metal species. Organometallic species of the elements tin, mercury and lead have been determined. The species have been extracted together from the wet sediments using hexane after an in-situ ethylation with sodium tetraethylborate (NaBEt₄). Gas chromatography-inductively coupled plasma-mass spectrometry (GC-ICP-MS), a very sensitive hyphenated technique for multielemental speciation analysis, has been used for their separation and detection.     

Chlorinated di- and triphenylmethanes in sediments of the Mulde and Elbe rivers

Congeneric groups of chlorinated diphenylmethanes (ClDPM) and triphenylmethanes (ClTPM) identified by coupled GC/MS investigations of Elbe and Mulde river sediments were not as yet noticed as environmental contaminants of aquatic sediments. ClDPM and ClTPM are structurally related to other polychlorinated aromatic compounds and form complex mixtures of congeners. Individual ClDPM/ClTPM as well as mixtures of congerers were synthesized, and served as reference compounds for isomer identification and quantitative analysis. In addition to mass spectra, GC/FTIR-investigations and retention indices proved to be valuable for structural assignments. Sediments from the Mulde river contained up to 220 μg/kg ClTPM and 170 μg/kg ClDPM. The spatial distribution of ClDPM/TPM concentrations indicated a strong localized source of emisson at the lower Mulde river, from where the compounds enter sediments and suspended matter of the Elbe river. The occurrence of ClTPM in the Hamburg harbour at comparable levels in samples of recent and older sediments indicates emissions over a prolonged period.     

Determination of thallium in sediments of the River Elbe using isotope dilution mass spectrometry with thermal ionization.

By using isotope dilution mass spectrometry with thermal ionization, TI concentrations were determined in sediments from six sampling positions of the River Elbe in the area of the former GDR (Bad Schandau, Dresden, Barby, Magdeburg, Werben/Havel and Cumlosen). For comparison, two samples from the River Rhine near Emmerich taken in 1978 and 1990 and the Community Bureau of Reference (BCR) certified reference material (CRM) 320 River Sediment were also analysed. Thallium concentrations after complete decomposition by high-pressure digestion (HNO3 + HF) and aqua regia [HCI-HNO3 (3 + 1)] ranged from 537 micrograms kg-1 in the BCR CRM 320 to 5192 micrograms kg-1 in the River Rhine sediment (1978) near Emmerich. The reproducibility of the method ranged from 0.06 to 4.7%. Only 49-94% of the total amount of TI was found after extraction with 1 mol dm-3 HNO3 and 43-86% after extraction with aqua regia. Sediments from Dresden, Barby, Werben/Havel and Cumlosen were found to have virtually identical TI concentrations as the River Rhine sediment sampled in 1990. In comparison with the extremely high Hg and As concentrations found in the River Elbe in an earlier study, the TI concentrations were not as high as expected.     

Polar organic compounds in the river Elbe — Development of optimized concentration methods using substance-specific detection techniques

Different methods for solid phase extraction (SPE) of polar, organic compounds found in Elbe water were compared. Mass-spectrometric detection (MS) after liquid chromatographic separation (LC) or flow injection analysis (FIA) and thermospray ionization (TSP) was used to assess the concentration behaviour as well as the detection techniques. A selected compound was identified using tandem mass spectrometry (MS/MS) carrying out mixture analysis.     

Phthalhydrazide nanoparticles as new highly reusable organic photocatalyst in the photodegradation of organic and inorganic contaminants

Phthalhydrazide nanoparticles are introduced as a new, efficient, stable and reusable organic photocatalyst for the photodegradation of a range of azo dyes, including methyl orange, methyl red, congo red and yellow titan, 4‐nitrophenol and permanganate as important organic and inorganic contaminants. Various experimental parameters including pH, photocatalyst dose, dye concentration and illumination time were investigated for methyl orange as a model substrate. The results revealed high degradation efficacy, up to 93.6%, for methyl orange in 20 min. Moreover, a preliminary kinetic study along with a proposed photodegradation mechanism is included in this study. Mechanistic investigations showed that phthalhydrazide behaved as a photoreduction catalyst. With the addition of Cl^? ion, as a hole scavenger, photodegradation efficacy for methyl orange was improved. Results showed that phthalhydrazide nanoparticles behaved better than commercial bulk phthalhydrazide and both performed as successful photocatalysts for photoreduction of the mentioned organic and inorganic compounds.     

Pesticides and other organic micro pollutants in the river Elbe

The main components of organic micro pollution regularly found in the river Elbe, belong to the wide spectrum of pesticides, nitro and chloro benzenes and the chelating agents, especially ethylenediaminetetraacetic acid (EDTA). The level of organic micro pollution with pesticides and the other organic micro pollutants in the upper and middle reaches of the river Elbe between Schmilka and Wittenberge was determined over a period of nearly three years. Four sample preparation methods (SPE: solidphase extraction and LLE: liquid-liquid extraction both with and without derivatization) have been used to analyze a wide spectrum of pesticides with different polarities by GC/ECD, NPD and MS. The pesticide pollution caused by the triazines decreases significantly from 0.35 g/l (mean value) in 1992 up to 0.15 g/l (mean value) in 1994. The correlation with the river water flow shows the diffuse character of the triazine input. In the last year of the pesticide screening a change to the more polar substances such as phenoxyalkanoic acid and nitrophenol pesticides as well as chloralkanoic acid pesticides have been noticed. The origin of trichloroacetic acid (TCA) can be explained by the waste influence, supported by the good correlation of the TCA course with the chloroform concentrations determined.     

Extraction chromatography of common anions in liquid-liquid anion exchange systems. Part. III. Monobasic aliphatic organic acids and their sodium salts as eluants

Summary The chromatographic behaviour of anions on paper strips treated with tri-n-octylamine (TOA) salts or Aliquat 336 and developed with aqueous solutions of acetic, formic, monochloroacetic or trifluoroacetic acids and their sodium salts was investigated. Liquid-liquid extraction of organic acids by 0.1 M solution of TOA in benzene as well as the anion exchange between benzene solutions of TOA salts or Aliquat 336 (in acetate form) in benzene and aqueous solutions of sodium halides was also studied. It was found that extraction increases in the following order of the acids: CH₃COOOH<HCOOH<CH₂CICOOH<CF₃COOH; the relative affinity of organic anions to the quaternary alkyl-ammonium cation also increase in a similar order. The extraction of acid in excess over the amount necessary to neutralize the amine was observed for all four acids. The R_F values of anions investigated depend markedly on the type of organic acids or their salts and their concentration in the mobile phase. Halide ions are more strongly retained on paper treated with Aliquat 336 as compared with TOA salts. The chromatographic systems investigated offer many possibilities to separate various anion mixtures.Parts and II: refs. [1, 2].     

Occurrence of synthetic hormones in sewage effluents and Langat River and its tributaries,Malaysia

This study investigated for the first time the occurrence of selected synthetic hormones including 17α-ethinylestradiol, levonorgestrel, norethindrone and cyproterone acetate in Malaysian tropical waters. Samples were collected from the effluents of five sewage treatment plants (STPs) and at seven stations along the Langat River in Selangor, Malaysia, and its main tributaries. Samples were extracted by solid phase extraction (SPE) and analyzed by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). In Langat river samples, only levonorgestrel and cyproterone acetate were found at 50% and 3.3% frequency. The concentrations detected for levonorgestrel ranged from less than the method detection limit (<MDL) to 213?ng?L^?1 and from?<?MDL to 76?ng?L^?1 for cyproterone acetate. For the STP effluent samples, levonorgestrel was <MDL in all samples and the concentrations detected were in the range?<?MDL – 262?ng?L^?1 for cyproterone acetate,?<?MDL ?11336?ng?L^?1 for norethindrone and?<?MDL – 1898?ng?L^?1 for 17α-ethinylestradiol.