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.     

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.CHC = , , -HCH, HCB, Pentachlorobenzene, Aldrin, Dieldrin, Heptachlor, Heptachlorepoxide, Octachlorostyrene, 4,4-DDE, 4,4-DDD, 4,4-DDT, PCB 28, PCB 52, PCB 101, PCB 138, PCB 153, PCB 180     

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.     

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.     

Characteristic levels of chlorinated hydrocarbons and trace metals in fish from coastal waters of North and Baltic sea

During investigations on the occurrence and distribution of contaminants in coastal waters of the North Sea and the Baltic organochlorine compounds such as hexachlorobenzene (HCB), octachlorostyrene (OCS), hexachlorocyclohexane isomers (HCH), dichlorodiphenyltrichloroethane (p,p'-DDT) and its metabolites and polychlorinated biphenyls (PCBs) and heavy metals such as mercury, cadmium and lead were determined in a selected flatfish species (flounder, Platichthys flesus L.). The sampling network covered the outer estuaries of the rivers Weser and Elbe, the German Bight, the Danish North Sea coast and coastal regions of the south-western Baltic. Organochlorine compounds were determined by high-resolution glass capillary gas chromatography with electron capture detector after sample pretreatment and clean up. For the determination of heavy metals a multi-stage analytical procedure was used, in which graphite furnace (for Cd and Pb) resp. cold vapour (for Hg) atomic absorption spectrometry was combined with pre-instrumental separation and enrichment techniques. Evaluation of the data from the programme made obvious significant geographical differences in the levels and the pattern with regard to the substances involved. For HCB, OCS and Hg a crucial point of contamination within the German Bright was recognized that was apparently influenced to a large extent by the inflow of waters from the Elbe.     

Organochlorine Pesticides and PCBs In Tissues from Dutch Citizens (1968–1986)

Abstract

Adipose tissue, milk and blood from Dutch citizens have been investigated for the occurrence of organochlorine compounds since 1968. In this paper, median values for HCB, α-HCH, β-HCH, γ-HCH, β-Hepo (heptachlorepoxide), dieldrin, p.p′-DDE, o.p′-DDT, TDE and PCBs (first determined by the perchlorination method, later by a selection of individual congeners) are given. Time trends, influence of age and sex of the donors, changes in concentrations of milk during lactation, the possible effect of life-style, and statistical evaluation of the data collected over the past twenty years will be discussed.

PCBs and p.p′-DDE occur in the highest concentrations in all tissues investigated, followed by HCB and β-HCH. Especially the p.p′-DDT levels decreased dramatically over the years of the investigation. Blood/fat accumulation factors were derived; they decrease in the order PCBs?p.p′-DDE >β-HCH?HCB > β-Hepo?dieldrin > α-HCH?γ-HCH.     

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.     

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     

Levels and patterns of polychlorinated biphenyls in water collected from the San Francisco Bay and Estuary, 1993–95

Levels of polychlorinated biphenyls (PCBs) were measured in water (particulate and dissolved fractions) from various locations in the San Francisco Estuary over the years 1993–1995 during six cruises. Geometric mean levels of ΣPCBs (sum of 58 congeners) in the combined dissolved and particulate fractions for the six cruises ranged from 340?ng/L to 1600?ng/L. Comparing this data to previous data from 1975 and 1980 does not reveal any significant temporal trends. The partitioning of PCBs into the dissolved/particulate fraction were correlated with total suspended solids. Using the novel chemometric technique of polytopic vector analysis (PVA) on the data from cruise 8 (April 1995), five separate PCB congener fingerprints were identified in the data. Fingerprint 1 (or end-member 1) represents a slightly degraded source of Aroclor^® 1260 in the northern part of the South Bay; the end-member (EM) 2 fingerprint is related to a predominantly Aroclor^® 1260 source that has been moderately-severely degraded present in the highest proportions in the Pacific Ocean sample; EM-3 is interpreted as a slightly degraded Aroclor^® 1242:1254:1260 mixture in southern San Pablo Bay; end-member 4 is interpreted as a moderately degraded source of multiple Aroclors^® and is present in the river samples; EM-5 is interpreted as a slightly degraded Aroclor^® 1254/1260 mixture present in northern San Pablo Bay and the South Bay.     

Levels and patterns of polychlorinated biphenyls in water collected from the San Francisco Bay and Estuary, 1993–95

Levels of polychlorinated biphenyls (PCBs) were measured in water (particulate and dissolved fractions) from various locations in the San Francisco Estuary over the years 1993–1995 during six cruises. Geometric mean levels of ΣPCBs (sum of 58 congeners) in the combined dissolved and particulate fractions for the six cruises ranged from 340 ng/L to 1600 ng/L. Comparing this data to previous data from 1975 and 1980 does not reveal any significant temporal trends. The partitioning of PCBs into the dissolved/particulate fraction were correlated with total suspended solids. Using the novel chemometric technique of polytopic vector analysis (PVA) on the data from cruise 8 (April 1995), five separate PCB congener fingerprints were identified in the data. Fingerprint 1 (or end-member 1) represents a slightly degraded source of Aroclor^? 1260 in the northern part of the South Bay; the end-member (EM) 2 fingerprint is related to a predominantly Aroclor^? 1260 source that has been moderately-severely degraded present in the highest proportions in the Pacific Ocean sample; EM-3 is interpreted as a slightly degraded Aroclor^? 1242:1254:1260 mixture in southern San Pablo Bay; end-member 4 is interpreted as a moderately degraded source of multiple Aroclors^? and is present in the river samples; EM-5 is interpreted as a slightly degraded Aroclor^? 1254/1260 mixture present in northern San Pablo Bay and the South Bay. Received: 21 March 1997 / Revised: 23 May 1997 / Accepted: 28 May 1997     

A pilot study on levels of organochlorine compounds in human milk in Nigeria

Concentrations of some persistent organochlorine compounds (OCC) in human milk samples from Nigeria are determined. Apart from the commonly detected insecticide residues in Nigerian environment (DDT-complex, HCH-isomers and HCB), polychlorinated biphenyls (PCBs) were also found in four out of the thirty-five samples analysed; the values varied from 0.32-0.62 mg/kg milk fat. In general, concentrations of the insecticides were low. p,p'-DDD was not detected in appreciable and quantifiable levels.     

Water pollution screening by large-volume injection of aqueous samples and application to GC/MS analysis of a river Elbe sample

The large-volume sampling of aqueous samples in a programmed temperature vaporizer (PTV) injector was used successfully for the target and non-target analysis of real samples. In this still rarely applied method, e.g., 1 mL of the water sample to be analyzed is slowly injected direct into the PTV. The vaporized water is eliminated through the split vent. The analytes are concentrated onto an adsorbent inside the insert and subsequently thermally desorbed. The capability of the method is demonstrated using a sample from the river Elbe. By means of coupling this method with a mass selective detector in SIM mode (target analysis) the method allows the determination of pollutants in the concentration range up to 0.01 μg/L. Furthermore, PTV enrichment is an effective and time-saving method for non-target analysis in SCAN mode. In a sample from the river Elbe over 20 compounds were identified. Received: 17 June 1996 / Revised: 22 November 1996 / Accepted: 25 November 1996     

Water pollution screening by large-volume injection of aqueous samples and application to GC/MS analysis of a river Elbe sample

The large-volume sampling of aqueous samples in a programmed temperature vaporizer (PTV) injector was used successfully for the target and non-target analysis of real samples. In this still rarely applied method, e.g., 1 mL of the water sample to be analyzed is slowly injected direct into the PTV. The vaporized water is eliminated through the split vent. The analytes are concentrated onto an adsorbent inside the insert and subsequently thermally desorbed. The capability of the method is demonstrated using a sample from the river Elbe. By means of coupling this method with a mass selective detector in SIM mode (target analysis) the method allows the determination of pollutants in the concentration range up to 0.01 μg/L. Furthermore, PTV enrichment is an effective and time-saving method for non-target analysis in SCAN mode. In a sample from the river Elbe over 20 compounds were identified. Received: 17 June 1996 / Revised: 22 November 1996 / Accepted: 25 November 1996     

Improvement, quality assurance and analytical results on the river Elbe contamination in the Czech Republic

Environmental analysis at trace levels is a new field of research in the Czech Republic since about ten years. New methods have to be adapted, pollution sources have to be investigated and quality assurance has to be established. The improvement in the detemination of trace substances in the Elbe river, mainly that of organic pollutants, is shown. A first insight on an international level is given into the origin of pollution in the Czech part of the Elbe river and the analytical work provided by the Czech water research institute and one of the most important monitoring laboratories.     

Photometric determination of dissolved oxygen with iron(II) cacotheline oxalate blue

Iron (II)-cacotheline-oxalate blue solution is used as reductometric reagent for the estimation of dissolved oxygen. By titrating the blue complex solution photometrically, the dissolved oxygen in water samples can be accurately determined in the range of 2 to 8 mg/l. The stoichiometry of the reaction between dissolved oxygen and the blue complex was found to be 1:0.8 or 5:4. The applicability of this method to distilled water, river water and reservoir water was tested.The Winkler's method [1] and its various modifications and adaptations, widely used for the determination of dissolved oxygen, are laborious and time consuming. Therefore a new method using iron (II)-cacotheline-oxalate (ICO) blue solution was developed for this purpose.     

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.     

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.     

Geochemical behaviour of major and trace elements in dissolved and particulate phases of the Bouregreg river (Morocco)

The Bouregreg river is one of the main rivers of Morocco, Its source being located in the Moroccan Central Massif and flows towards the Atlantic coast through the coastal Meseta. The Bouregreg river basin is located in the Moroccan Central Massif which consists mainly of Palaeozoic formations that were subject to the Hercynian orogeny. To evaluate the environmental status of the Bouregreg river water, sampling of the dissolved (<0.22 μm) and suspended (>0.22 μm) phases was performed at 10 sites along the Bouregreg river and its tributaries in the winter of 2005. Major (Na, Ca, K, Ti, Mn, Al and Fe), trace (As, Ba, Bi, Cd, Co, Cr, Cs, Cu, Hf, Li, Mo, Nb, Ni, Pb, Rb, Sb, Sc, Sn, Sr, Ta, Th, U, V, W, Y, Zn and Zr) elements and rare earth elements were analysed. The dissolved and particulate phase of the Bouregreg river draining these contrasting zones show similar characteristics to those observed in other major tropical rivers such as the Congo and Amazon, and vary in composition between the different source areas. Obtained data show that the spectra of the standardized concentrations for all the determined elements in the dissolved and the suspended phase have the same form whatever the station and that the whole of the elements is strongly deficient compared to the upper continental crust. The strong depletion in the suspended phase and the associated enrichment in the dissolved phase suggest that some elements such as Rb, Ba and Sr are the most mobile elements during the weathering processes. The removal of the most mobile elements from the bedrock concentrates all remaining elements in the weathered phases of the soils, from whence it can be removed mechanically. As and Sb are strongly enriched as well in the dissolved load as in the suspended load.     

Monitoring of total Hg in the river Elbe: FIA-device for on-line digestion

The development of an apparatus for the on-line sampling, digestion and quantification of total mercury in surface water is described. Detection and quantification is done by flow injection cold vapor atomic absorption spectroscopy (FI-CVAAS). Three digestion methods were tested, chemical, microwave and UV. The influence of the digestion parameters (digestion method, digestion time, microwave power, concentration of oxidation solution) on the recovery of mercury in water of the river Elbe have been investigated. Mercury can be determined almost quantitatively (recovery rate > 85%) with some digestion procedures described. The best results were reached by UV digestion. The technique is fast, simple to handle and robust. Each complete analysis only take four minutes. The working range is 10 to 1000 ng/L. The measuring arrangement has been applied successfully in a governmental monitoring station at Schnackenburg/Elbe, Germany.