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     

Quantification of polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB) in the picogram/liter range in water of the river Elbe

Sampling and determination of dissolved and particlebound PCBs and HCB in the river Elbe are described. A new filtration/adsorption unit for sampling of dissolved lipophilic contaminants was developed. The detection limit for dissolved PCBs and HCB was 5 pg/l. The data show that more than 98% of the PCBs and of HCB in the water of the river Elbe are particle-bound.     

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.     

Semivolatile organic compounds — polychlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF), biphenyls (PCB), hexachlorobenzene (HCB), 4,4'-DDE and chlorinated paraffins (CP) — as markers in sewer films

A municipal sewer system has been investigated for the sources of a set of semivolatile compounds, such as polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF), polychlorinated biphenyls (PCB), hexachlorobenzene (HCB), 1,1-dichloro-2,2-bis(p-chlorophenyl)-ethene (4,4'-DDE), and chlorinated paraffins (CP), using sewer films as the sampling medium. A cleanup method for these semivolatile compounds in sewer films is described. The project has been undertaken for the differentiation and localization of specific inputs of xenobiotics from defined regions of the city. A unique pattern of PCDD/PCDF found in sewage sludge has led to the search for a specific source within the sewer system, which has finally been localized as a distinct plant. Other organochlorine compounds proved to be significant indicators for industrial and domestic sewers. PCB appeared as an industry correlated parameter, while 4,4'-DDE indicated domestic sewers. Chlorinated paraffins have been detected in the mg/kg range and are markers and indicators for metal-working industries. Finally, the release of CP by the sewage treatment plant, into the nearby river, has been investigated.     

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.     

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.     

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.     

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     

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.     

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.     

Study of the interference problems of dioxin-like chemicals with the bio-analytical method CALUX

The reporter gene expression method CALUX has proven to be a very valuable screening technique for assessing toxic equivalents of dioxins and dioxin-like compounds, because it detects all AhR ligands in a variety of sample matrices. However, the exact meaning of the CALUX response is difficult to evaluate for complex mixtures mainly since not all AhR ligands are known and since antagonistic or synergistic effects occurs.

In this paper, non-additive effects on the CALUX response of dioxins were investigated for a limited number of dioxin-like compounds in concentration ranges that are 10²–10⁸ times higher than that of 2,3,7,8-TCDD. Antagonistic effects are detected for three Aroclors (1242, 1254, 1260), Halowax 1014 (PCN), HCB and PBB 169. The ratios, Aroclor/dioxin, Halowax/dioxin and HCB/dioxin, needed to observe an antagonistic effect are 10 000, 5000 and 50 000, respectively. No significant deviation from additivity was observed for Aroclor 5442 (PCT) and PBB 77 in the concentration range investigated.

Two clean-up procedures have also been tested: in some cases the non-additive effects disappeared or were strongly reduced. Using only an acidic silica column, the classical dioxin-like compounds investigated here (PCB, PCT, PBB, PCN, HCB) as well as the dioxins are collected and analyzed altogether in one fraction. Consequently, no major alteration of the non-additive effects is expected. An acidic silica column combined with an activated carbon column allows the separation of PCDD/F and dioxin-like PCB in two different fractions, PBB 169 is completely eluted in the dioxin fraction and PBB 77 is distributed between the PCB and dioxin fraction. HCB is completely separated from the PCDD/F fraction.     

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.     

Mercury-cycling in surface waters and in the atmosphere — Species analysis for the investigation of transformation and transport properties of mercury

The river Elbe has been one of the most contaminated rivers with regard to mercury for many years. In 1991 a length-profile has been measured for mercury and methylmercury (CH₃Hg⁺) from Obristvi, Czech Republic, to the German bight. Total mercury has been measured by cold vapor atomic absorption spectrometry (CVAAS). The organo mercury compounds have been separated by high performance liquid chromatography (HPLC) connected on-line to an atomic fluorescence spectrometer (AFS) by a continuous flow-system. Total mercury up to 120 mg Hg⁺/kg and CH₃Hg⁺ concentrations up to 130 μg CH₃ Hg⁺/kg could be detected in special sites. The formation of CH₃Hg⁺ in sediments can be caused besides the methylation of mercury, by sulphate reducing or methanogenic bacteria and transmethylation reactions with organometals. Atmospheric mercury concentrations have been measured at three different European sites. Samples have been collected on goldcoated glass balls or on quartz wool, respectively. After thermal desorption mercury has been determined using the two step amalgamation technique with AFS detection. Compared to natural background concentrations of total gaseous mercury (TGM), slightly increased levels could be detected at a rural site in Germany. This increase can probably be explained by long-range transport processes. Within the vicinity of a inactivated mercury production plant high concentrations of up to 13.5 ng/m³ particle associated mercury (Hg_part) have been detected. Consequently, dry deposition of mercury in the particulate form can intensify the total deposition flux close to Hg-emitting sources.     

Assessment of the main natural radionuclides,minor and trace elements in soils and sediments of the Shu valley (near the border of Kazakhstan and Kyrgyzstan)

New data on the concentrations of the main gamma-emitting radionuclides, minor and trace elements, and isotopes of uranium (with Ra-226 as a daughter product of U-238) and thorium in soils and sediments of the Shu valley (from the river Chon-Kemin to the river Kuragatty downstream the river Shu) are presented, determined by high-resolution gamma-spectrometry, k ₀-instrumental neutron activation analysis and alpha-spectrometry with appropriate radiochemical separations of the samples, respectively. The results obtained showed an aquatic migration pathway of most of the trace elements and radionuclides and predicted water pollution downstream the river Shu. The scandium method showed pollution by As, Br, Ca, Cr, Zr of the Tasotkel dam impoundment and by Ca and Cr of the river Shu below its confluence with the river Kuragatty. According to the disequilibrium isotopic method for uranium (using the isotopic ratio U-234/U-238), areas with accumulation and leaching processes were estimated for soils and sediments of the river Shu and its main inflows.     

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.     

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.     

Determination of polychlorinated dibenzo-p-dioxin and dibenzofuran congeners in air particulate and marine sediment standard reference materials (SRMs)

Due to the limited number of environmental matrix certified reference materials (CRMs) with assigned values for natural levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), an interlaboratory study was undertaken by the National Institute of Standards and Technology (NIST) and Environment Canada to establish reference concentration values for selected PCDD/Fs in two well-characterized NIST Standard Reference Materials (SRMs): SRM 1649a (Urban Dust) and SRM 1944 (New York/New Jersey Waterway Sediment). Results from 14 laboratories were used to provide reference values for the seventeen 2, 3, 7, 8-substituted PCDD/F congeners, the totals for individual tetra- through hepta-substituted PCDD/F homologues, and the total amount of tetra-through hepta-substituted PCDD/Fs. The mass fractions for the individual 2, 3, 7, 8-substituted congeners range from approximately 0.01 μg/kg to 7 μg/kg dry mass.     

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.     

Size fractionation of marine sediments by pinched inlet gravitational split-flow thin fractionation and the study of size dependent PCDD/Fs concentrations from different bay areas

Pinched inlet gravitational split-flow thin fractionation (PI-GSF) has been applied to the continuous size fractionation of marine sediments in order to study the difference in sediment size distribution and the concentration of PCDD/Fs contained in different particle sizes. A PI-GSF channel, known to improve the separation efficiency by reducing the sample inlet thickness, was utilized to fractionate sediments collected from three different bay areas (Geoje, Ulsan, and Pohang) in Korea into 5 different sub-populations (<2.0, 2.0-5.0, 5.0-10, 10-20, 20-63 microm in diameter). The sorted sediment fractions from PI-GSF were examined using electron microscopy to obtain size distribution and the results showed a variation in particle size distribution between bay areas. When the collected particle fractions were examined for size dependent levels of PCDD/Fs, the concentrations of total PCDD/Fs were shown to be much greater for samples collected close to heavy industry complexes than sediments from bay areas without major industry.