Investigations on sample pretreatment for the determination of selected metals and organochlorine compounds in suspended particulate matter of the River Elbe

The River Elbe and some of its tributaries are transporting polluted suspended particulate matter (SPM). Due to the property of SPM to accumulate anthropogenic and nonanthropogenic substances, this matrix is of interest from an analytical point of view. SPM has been collected in 13 sampling devices, placed in monitoring stations along the River Elbe from the Czech border to the North Sea and the embouchures of its tributaries Schwarze Elster, Mulde and Saale. Characterization of the SPM has been carried out by sieving and determining the content of total carbon. Comparative studies with different digestion procedures are presented for the determination of heavy metals and arsenic in the fine grain particle size <20 m of freeze-dried SPM. In a first test the highest concentrations have been found for microwave heating in a closed system when using an acid mixture of HNO₃/HF 3:1. Results of an interlaboratory test show the good practicability of the microwave heating digestion method. The determination of organochlorine compounds in a freeze-dried sample by three different extraction methods including supercritical fluid extraction (SFE) with CO₂ shows that the highest extraction efficiency is found for the conventional Soxhlet method.     

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.     

N-/P-pesticides in the Czech and German part of the river Elbe — Analytical methods and trends of pollution

A GC/MS screening procedure and an analytical routine method with GC/NP-detection is described for N-/P-pesticides in the river Elbe. The GC/MS screening procedure allows the separate analysis of pesticides in suspended particulate matter (SPM) and water (centrifugate). For the pesticides identified only a negligible (<1%) amount was bound to SPM compared to the “dissolved” amount in the centrifugate. N-/P-pesticide concentrations as time series and Elbe length-profiles are presented showing a drastical decrease of the pesticide pollution of the Elbe from 1989 to 1994. Major compounds were dimethoate, parathion-methyl, atrazine and simazine found in the μg/l range in the Elbe downstream of its tributary Mulde obviously stemming from a former East German pesticide production site.     

Uranium in water of the Mulde River

The Mulde River is a left side tributary of the Elbe River and mainly situated in Saxony. The river system consists of the Freiberger Mulde River and the Zwickauer Mulde River, which merge to form the Vereinigte Mulde River. The Zwickauer Mulde River drains the former uranium mining and milling areas in Saxony. This research project was established to quantify the long-term effect of the former uranium mining and milling activities by investigating the content of uranium of the water of the Mulde River. The activity concentration of uranium in samples from the Zwickauer Mulde River is still high compared with the natural background. The values measured in the water of the Vereinigte Mulde River are also elevated, but to a lesser extent due to the dilution effect caused by the merging with the uncontaminated Freiberger Mulde River. Furthermore, the level of contamination of the river water decreased by at least a factor of three as compared to the early 1990s.     

Polychlorinated dibenzodioxins and dibenzofurans in suspended particulate matter of the River Elbe 1994

In April/May 1994 during a period of high discharge in the German part of the River Elbe (9 stations) and its main tributaries (3 stations) samples of suspended particulate matter (SPM) have been collected by means of sedimentation chambers with sampling periods of three or four weeks. Subsequent analyses for polychlorinated dibenzodioxins and dibenzofurans (PCDD/F) have shown that the river enters Germany with a rather low PCDD/F-load which almost steadily increases to below Hamburg. Major sources of contaimination has been the input by the tributary Mulde and resuspension of contaminated sediments along the riversides. Downstream of Hamburg marine influence have caused a sharp decrease of PCDD/F-contents. Changes in the result of 1989, 1992/93 have been discussed.     

Organotins: their analysis and assessment in the Elbe river system, Northern Germany

Organotins have been analyzed using a new derivatisation technique in wet sediments by ethylation with NaBEt₄ and a GC/AAS coupling for separation and detection. In this way the Sn(IV) and the monoalkylated compounds could also be analysed more easily than by the Grignard derivatisation method used by other authors. Organotins are present not only as expected in the harbours, shipyards and the pleasure boat areas but also in the river itself, upstream of these places. Ships are thus not the only sources. An organotin production plant on the banks of a tributary, the Mulde river, is characterised by high tetrabutyltin and lower tributyltin amounts along the river to its mouth over 350 km away. The concentrations are up to 14 mg tetrabutyltin (Sn)/kg sediment. The superimposed patterns are from ship antifouling paints, characterised by a high content of tributylin in different stages of degradation to di and monoalkylated compounds; this shows the bacterial degradation possibilities for organotins in the river. In general, organometallics are a contaminant of great concern in the Elbe river system.     

Chloro-bis-propyl Ethers in the Elbe River – Isomeric Distribution and Enantioselective Degradation

Cyclodextrin derivatives are evaluated as chiral stationary phases for the enantiomer separation of chlorinated bis(propyl) ethers (BPE). The enantiomeric composition of the 2,3,2′,3′- and 1,3,2′,3′-isomers of tetrachlorobis(propyl) ether in the Elbe River has been quantitatively determined by enantioselective gas chromatography and coupled gas chromatography/mass spectrometry in selected-ion-monitoring mode. Significant enantiomeric discriminations are observed in selected water samples, indicating that enantioselective bio-degradation mechanisms are at least partly responsible for the overall degradation processes.     

Quantitative description of element concentrations in longitudinal river profiles by multiway PLS models

Partial least squares (PLS) models were used to examine the relationships between the distributions of elements in different compartments of a river. These relationships, if existing, enabled predictions to be made of the element concentrations in one compartment by knowing the concentrations in another compartment. The subjects of the study were the element concentrations measured in the water and the sediment of the river Saale as well as in the water and the suspended matter of the river Elbe. Special emphasis was placed on a comparison between two-way and three-way PLS.     

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     

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     

Quantitative description of element concentrations in longitudinal river profiles by multiway PLS models

Partial least squares (PLS) models were used to examine the relationships between the distributions of elements in different compartments of a river. These relationships, if existing, enabled predictions to be made of the element concentrations in one compartment by knowing the concentrations in another compartment. The subjects of the study were the element concentrations measured in the water and the sediment of the river Saale as well as in the water and the suspended matter of the river Elbe. Special emphasis was placed on a comparison between two-way and three-way PLS. Received: 13 March 1998 / Revised: 29 October 1998 / Accepted: 17 November 1998     

Mass spectrometric investigations of water extracts of the river Elbe for the determination of potential inputs of pollutants into the North Sea

A non-target screening by gas chromatography-mass spectrometry has been carried out on water extracts of the river Elbe in order to obtain an overview of organic compounds being dissolved or bound to suspended matter in the Elbe. Samples of 1001 volume were taken at the freshwater border at Stade and extracted by liquid-liquid extraction with pentane. Before GC-MS analysis, the water extracts were fractionated into 15 subsamples by HPLC on an SiO₂ column. A sensitivity of ca. 50 to 250 pg/l was reached for the GC-MC analysis. Several hundreds of natural and anthropogenic compounds could be identified or at least grouped into a compound class. The presence of a number of compounds could be verified from earlier investigations, in addition a great number of anthropogenic compounds were described which have previously not been reported for the river Elbe.     

Environmetric modeling and interpretation of river water monitoring data

This environmetric study deals with modeling and interpretation of river water monitoring data from the basin of the Saale river and its tributaries the Ilm and the Unstrut. For a period of one year of observation between September 1993 and August 1994 a data set from twelve campaigns at twenty-nine sampling sites from the Saale river and six campaigns from the river Ilm at seven sampling sites and from river Unstrut at ten sampling sites was collected. Twenty-seven chemical and physicochemical properties were measured to estimate the water quality. The application of cluster analysis, principal components analysis, and apportioning modeling on absolute principal components scores revealed important information about the ecological status of the region of interest:identification of two separate patterns of pollution (upper and lower stream of the rivers);identification of six latent factors responsible for the data structure with different content for the two identified pollution patterns; anddetermination of the contribution of each latent factor (source of emission) to the formation of the total concentration of the chemical burden of the river water.As a result more objective ecological policy and decision making is possible.     

Analysis of heavy metals and sulphur-rich compounds in the water moss Fontinalis antipyretica L. ex Hedw.

The water moss Fontinalis antipyretica has been investigated to estimate heavy metal pollution in the river Elbe (middle Germany). Procedures of plant separation, digestion as well as an analytical method for ICP-MS analyses have been evaluated. Reproducibility and accuracy have been demonstrated on BCR 61 (NIST) reference material and results have been compared with AAS and AES data. The distribution of heavy metals in different plant segments of indigenous material has been analyzed. Exposition of plant material in the river Elbe have shown no correlation between the heavy metal content in plants and that of water samples. Cd and Zn concentrations found in the plant material are significantly enriched relatively to control samples. To understand the sophisticated ‘real system’ experiments have been carried out under laboratory conditions to investigate induced sulphur-rich compounds in the presence of heavy metals using HPLC including on-line derivatization.     

Chlorinated hydrocarbons- (CHC) and PCDD/F-levels in sediments and breams (Abramis brama) from the river Elbe (contribution to the German Environmental Specimen Banking)

Chlorinated hydrocarbons have been determined in sediments and breams (Abramis brama) from different locations along the river Elbe, starting from the border to the Czech Republic down-stream up to Cumlosen (river km 470), near the frontier of the former German Democratic Republic. High levels of hexachlorobenzene (HCB) have been found in sediments. HCB, DDT-metabolites and octachlorostyrene (OCS) have been the most dominant compounds in bream, especially fish from eastern sampling sites have been heavily contaminated. Furthermore, sediments from 1991–1993 have been analysed to determine polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F). The CHC-burden of the river Elbe declines downstream, whereas the PCDD/F-content increases in that direction.     

In-situ methylation of strongly polar organic acids in natural waters supported by ion-pairing agents for headspace GC-MSD analysis

Strongly polar organic substances like halogenated acetic acids have been analyzed in surface water and groundwater in the catchment area of the upper Elbe river in Saxony since 1992. Coming directly from anthropogenic sources like industry, agriculture and indirectly by rainfall, their concentrations can increase up to 100 μg/L in the aquatic environment of this catchment area. A new static headspace GC-MSD method without a manual pre-concentration step is presented to analyze the chlorinated acetic acids relevant to the Elbe river as their volatile methyl esters. Using an ion-pairing agent as modifier for the in-situ methylation of the analytes by dimethylsulfate, a minimal detection limit of 1 μg/L can be achieved. Problems like the thermal degradation of chlorinated acetic acids to halogenated hydrocarbons and changing reaction yields during the headspace methylation, could be effectively reduced. The method has been successfully applied to monitoring bank infiltrate, surface water, groundwater and water works pumped raw water according to health provision principles. Received: 17 July 1997 / Revised: 29 September 1997 / Accepted: 2 October 1997     

In-situ methylation of strongly polar organic acids in natural waters supported by ion-pairing agents for headspace GC-MSD analysis

Strongly polar organic substances like halogenated acetic acids have been analyzed in surface water and groundwater in the catchment area of the upper Elbe river in Saxony since 1992. Coming directly from anthropogenic sources like industry, agriculture and indirectly by rainfall, their concentrations can increase up to 100 μg/L in the aquatic environment of this catchment area. A new static headspace GC-MSD method without a manual pre-concentration step is presented to analyze the chlorinated acetic acids relevant to the Elbe river as their volatile methyl esters. Using an ion-pairing agent as modifier for the in-situ methylation of the analytes by dimethylsulfate, a minimal detection limit of 1 μg/L can be achieved. Problems like the thermal degradation of chlorinated acetic acids to halogenated hydrocarbons and changing reaction yields during the headspace methylation, could be effectively reduced. The method has been successfully applied to monitoring bank infiltrate, surface water, groundwater and water works pumped raw water according to health provision principles.     

Mechanism of oxidation of aminoalkylphenol derivatives with benzoyl peroxide

Conclusions From the oxidation products of the methyl, ethyl, propyl, and butyl ethers of o-amino-p-tert-butyl-phenol using benzoyl peroxide were isolated and characterized 23 compounds, for 14 of which the structure was established. Schemes were proposed for the formation of the oxidation products.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2519–2523, November, 1972.     

Analysis of heavy metals and sulphur-rich compounds in the water moss Fontinalis antipyretica L. ex Hedw.

The water moss Fontinalis antipyretica has been investigated to estimate heavy metal pollution in the river Elbe (middle Germany). Procedures of plant separation, digestion as well as an analytical method for ICP-MS analyses have been evaluated. Reproducibility and accuracy have been demonstrated on BCR 61 (NIST) reference material and results have been compared with AAS and AES data. The distribution of heavy metals in different plant segments of indigenous material has been analyzed. Exposition of plant material in the river Elbe have shown no correlation between the heavy metal content in plants and that of water samples. Cd and Zn concentrations found in the plant material are significantly enriched relatively to control samples. To understand the sophisticated real system experiments have been carried out under laboratory conditions to investigate induced sulphur-rich compounds in the presence of heavy metals using HPLC including on-line derivatization.