M.T.J. Hillebrand

Koninklijk Nederlands Instituut voor Onderzoek der Zee - NIOZ, Burg, North Holland, Netherlands

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Publications (18)21.27 Total impact

  • Comparative Biochemistry and Physiology Part C Comparative Pharmacology and Toxicology 01/1998;
  • Marine Environmental Research - MAR ENVIRON RES. 01/1998; 46(1):533-534.
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    ABSTRACT: A new method is proposed to represent the qualitative and quantitative aspects of the complex mixtures of polychlorinated biphenyls in environmental samples. It is based on individual congener data. It involves the sum of concentrations of congeners (ΣPCB) and the percentage contributions of these congeners to ΣPCB. The concentration of each of the congeners in the sample is obtained from these numbers by a simple procedure. This generally applicable, concise and accurate information is useful for comparison purposes (trend analysis, monitoring, comparisons between different matrices), for research purposes (processes, effect studies, identification of sources, sinks and transport processes) and for contamination/pollution assessment purposes. It allows administrators to understand the scope and limitations of ΣPCB data and scientist to apply the information on individual congeners to other studies.
    Marine Pollution Bulletin. 01/1988;
  • M.Th.J. Hillebrand, R.F. Nolting
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    ABSTRACT: This article describes how sampling for micropollutants in the open ocean is carried out. It describes recent developments, discusses sampling problems due to the remarkably low concentrations of micropollutants. Special precautions required to prevent sample contamination are described.
    TrAC Trends in Analytical Chemistry 03/1987; 6(3):74–77. · 6.35 Impact Factor
  • M. Th. J. Hillebrand, R. F. Nolting
    TrAC Trends in Analytical Chemistry 01/1987; 6(3):74-77. · 6.35 Impact Factor
  • Source
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    ABSTRACT: The distributions of organochlorines in estuarine and marine systems, and in particular those of the individual PCB components have been analysed for the partitioning of these substances between water, particulate matter (seston), plankton, worms, shellfish, fish and some birds. The Kd concept, where Kd is the distribution coefficient in ml·g−1 units, has been used to investigate the distribution ratio between solid substrates and water. Additionally, an attempt has been made to determine the regression coefficient of Kds with a polarity index of the individual PCB components. Since the octanol-water partition coefficient (log Kow) is significantly proportional to the IUPAC Numbers of these components, this Kd-IUPAC Number regression has been carried out for samples from the Delta region, the North Sea and the Wadden Sea. For the latter two regions, existing concentrations from unpublished reports have been taken.Two major results have been obtained, while one important question remains to be answered: (i) Organochlorine (pesticides and ΣPCBs) concentrations in mussels can be successfully correlated to salinities of estuarine waters, if the sources of organochlorines are linked to the major fresh waters of the estuarine system. This correlation is independent of the seasonal changes in condition of these organisms by fat content, if the records is made for a period of two years. (ii) These results and those on Kd determinations demonstrate for aquatic organisms a degree of consistency in the Kd levels if concentrations in the organisms are calculated on fat basis. The Kd range for ΣPCBs is 105–106, independent of the area of investigation. The same is true for seston with a range of Kds of 104–105. (iii) A very interesting question involves the Kd-IUPAC Number regression coefficients and the value and sign (+ or −) of this coefficient. In general 60% of all correlations seem to be significant, but the different values and in particular the negative correlations are difficult to explain even when third-degree S-shape correlations are considered. A negative correlation implies a weaker adsorption of less-polar compounds (higher chlorinated PCBs with higher IUPAC Number), which cannot be explained by hydrophobic-hydrophylic reactions. An extended study on the true-dissolved organochlorines might be necessary to exclude errors which might be due to the methodology of filtration.
    Netherlands Journal of Sea Research. 01/1986;
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    ABSTRACT: Measurements of dissolved and suspended metals and organochlorine compounds were made in conjunction with hydrographic and sedimentological parameters at three fixed positions in different salinity regimes of the estuary of the Varde Å at regular intervals during a tidal cycle and during a survey in the adjacent Wadden Sea in August 1976.In the river, low concentrations of dissolved pentachlorobenzene (0.1 ng·1−1), hexachlorobenzene (0.1 ngsd1−1), polychlorinated biphenyls (1 ngsd1−1 Aroclor 1254 equivalent), α-hexachlorocyclohexane (2 ng·1−1), γ-hexachlorocyclohexane (2 ng·1−1) and a few yet unidentified compounds at simililarly low concentrations were detected. In the estuary, the only compounds present in concentrations above the limits of detection in 1-litre samples were the hexachlorocyclohexane isomers. In all samples, the amount of each isomer in solution was larger than in suspension. No evidence was found for transitions of these compounds between solution and suspension during estuarine mixing.The metals Cd, Zn and Fe were removed from solution in the early stages of estuarine mixing by sorption to freshly eroded sediment particles in the mud reach. Conservative behaviour was found for Cu. Manganese is cycled between particulate and dissolved forms. It is removed from solution in the lower estuary and produced in the upper part, mainly in response to variations in pH and resuspended sediment concentration, resulting in a maximum in the dissolved Mn concentration at low salinities.Elemental contents in seston in the estuary were determined primarily by mixing of particles from the lower estuary, the river and resuspended bottom sediments. These have different contents of organic C, organic N and metals. The relative contribution from originally dissolved metals is small. The variations in elemental contents could be explained in terms of a model involving a continuously suspended fraction, dominating at low seston concentrations, consisting of smaller, less dense particles with relatively high contents of Cd, Zn, Cu, Pb, Ca, Mg, organic C and organic N, and a fraction introduced by resuspension, consisting of larger, denser particles with higher contents of Mn, Al and Ti. Elemental contents and elemental/A1 ratios are nearly constant at seston concentrations above 20 mg·1−1. Elementaa content of Fe and Si did not vary with seston concentration. It is suggested that in addition to A1 silicates, other minerals such as Fe and Mn oxides and organic matter are important sites for particulate trace metals, especially in the continuously suspended fraction.
    Netherlands Journal of Sea Research. 01/1985;
  • J C Duinker, M T Hillebrand
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    ABSTRACT: The presence of polychlorinated biphenyls in the environment was discovered by JENSEN (1966), using techniques involving GLCseparations with packed columns. Essentially the same technique has been applied since in numerous analyses of these compounds carried out on a worldwide scale. The use of packed columns results in poor separation of the constituents of the usually complex PCB mixtures. The separations are often performed in an isothermal mode at about 200~ Under such conditions, relatively volatile compounds elute very early, thus appearing almost unresolved from each other as well as from other volatile compounds. The importance of early eluting PCB components has been overlooked in many reports. In combination with these packed column separations, qualitative and quantitative analyses were performed by comparison of chromatograms of sample extracts and of some technical formulation, e.g. Aroclor 1242, 1254 or 1260. The selection of the formulation to be used for comparison has been more art than science because as a rule, the chromatogram of an environmental sample differs from that of any of the formulations. The difficulties with early eluting components taken into account, it is understandable that
    Bulletin of Environmental Contamination and Toxicology 08/1983; 31(1):25-32. · 1.11 Impact Factor
  • J C Duinker, M T Hillebrand
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    ABSTRACT: Clophen A30, A40, A50, and A60 technical formulations were analyzed by electron capture (ECD) and mass spectrometric (MS) detection techniques, after gas chromatographic separation on one fused silica capillary column (SE-54). On the basis of combined ECD and MS data, most of the strong and many of the weaker peaks were identified on the basis of 102 individual PCB components, available as reference compounds. Several differences from previously published assignments that were based on retention index calculations were found. The available individual components accounted for 82-85% of the total PCB content in A30 and A40 and 91-100% in A50 and A60.
    Environmental Science and Technology 08/1983; 17(8):449-56. · 5.26 Impact Factor
  • J.C. Duinker, M.T.J. Hillebrand, J.P. Boon
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    ABSTRACT: Concentrations of organochlorines were determined in Macoma balthica, Arenicola marina, Crangon crangon and sediments from the Dutch Wadden Sea. Maximum concentrations of (total) PCB, γ-HCH and dieldrin were found in the western part; a pronounced maximum of HCB was found in the western part. Concentrations of PCB, p,p′-DDD and p,p′-DDE in sediment were correlated with the percentage of particles <50 μm. The relative contribution of each individual component to total PCB is very similar in Macoma and Arenicola and is independent of the concentration of total PCB. The relative concentrations of some components with structures facilitating metabolism, were lower in Crangon.The patterns of pentachloro- and higher chlorinated biphenyls were equal in Macoma, Arenicola and sediments. Since these components are not found in solution, they must be taken up from sediment and food.The results are in agreement with partitioning between body lipids and water as the dominant mechanism determining concentrations of persistent lipophilic contaminants in the animals. Partitioning with the ambient water may also determine the concentrations in the sediment.
    Netherlands Journal of Sea Research. 01/1983;
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    ABSTRACT: Attempts were made to determine the relative importance of chemical or physico-chemical processes and sedimentation and resuspension processes on the behaviour of metals (Cd, Zn, Cu, Pb, Cr, Mn, Fe, Ca, Al, Si, Ti, Mg), organic C and N and organochlorine compounds (α- and γ-hexachlorocyclohexane) in the estuarine region of the river Elbe in summer 1976. The latter processes seemed to be relatively less important than in some other estuaries. This may result from a much less pronounced mud shoal in the Elbe estuary. Such a mud shoal may act as a continuous source for tidal resuspension of bottom sediment particles. Alternating sedimentation and erosion resulted in systematic variations in the composition of suspended matter in terms of the relative contributions of two fractions. One fraction consisting of permanently suspended small and low-density particles having higher contents (weight to weight) of Cd, Zn, Cu, Pb, Cr, Mg and organic C and N. The other fraction consisting of resuspending larger and denser (mud) particles having higher contents of Mn, Fe, Al, Si and Ti.In addition to Al silicates, organic matter and Fe and Mn oxides may be important sites for trace elements (like Cd and Zn) in both fractions, but particularly so in the permanently suspended fraction.Evidence was found for the removal of Cd, Zn, Cu, Mn and Fe from solution into suspended particles during the initial phases of estuarine mixing. Estuarine mud, acting as sink for particulate pollutants, may thus accumulate originally dissolved components.A wide range of PCB components with high and low degrees of chlorination was present in solution as well as in suspension. Water was the most important carrier for components with low (and seston for those with high) degree of chlorination. Concentrations of individual PCB components ranged from picograms to nanograms per litre. The only compounds present in the estuary and the Wadden Sea above the detection limit in 1-litre samples were α- and γ-HCH, in the order of ng · 1−1.
    Netherlands Journal of Sea Research 01/1982; 15(2):141-169.
  • G EDER, W ERNST, H GOERKE, J DUINKER, M HILLEBRAND
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    ABSTRACT: Two laboratories analysed 12 organochlorine compounds in the same and parallel samples of 3 invertebrate species (Cerastoderma edule, Mya arenaria, Crangon crangon) obtained from the western Dutch Wadden Sea in 1976. The two different analytical methods used resulted in very similar mean residue levels. These levels deviated in only 2 out of 16 cases by more than 50%. The PCB levels predominated with 20 to 100 ng·g−1, and were higher than those of the same species from the Weser estuary, Germany. The other compounds ranged generally below 6 ng·g−1.
    Netherlands Journal of Sea Research 01/1981; 15(1):78-87.
  • Bulletin of Environmental Contamination and Toxicology 01/1981; 25(6):956-64. · 1.11 Impact Factor
  • J C Duinker, M T Hillebrand
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    ABSTRACT: The residue concentrationsin the fetus are of the same order of magnitude as the high values detected in specimens found dead along the Dutch coast (KOEMAN & VAN GENDEREN 1966, KERKHOFF & BOER 1977). The results suggest that a significant fraction of the body burden of organochlorines in the female can be transferred to the fetus. Sufficient material for analysis could only be obtained of kidney, liver and subcutaneous fat. Tissue extracts in n-pentane were cleaned up and fractionated as reported before (DUINKER & HILLEBRAND 1978). Identification and quantitation were done by electron capture gas chromatography on two columns of different polarities, p,p'-DDE was distinguished from the PCB peak with the same retention, by comparing chromatograms obtained before and after treatment of the extract with chromic acid, oxidizing p,p'-DDE and leaving PCB unchanged (Fig. i). No corrections for blanks were necessary. All components in the list of organochlorine concentrations (Table i) have been further identified by combined gas chromatography-mass spectro
    Bulletin of Environmental Contamination and Toxicology 01/1980; 23(6):728-32. · 1.11 Impact Factor
  • J.C. Duinker, M.Th.J. Hillebrand, R.F. Nolting
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    ABSTRACT: Maximum concentrations of PCB and members of the DDT family in liver, brains, kidney, spleen and heart and Cu, Pb, Zn and Cd in brains of harbour seals found dead in the Dutch Wadden Sea are higher than those reported for specimens from the German Wadden Sea, where the population is stable in contrast to the strong reduction observed for the population in the former part. Results are also compared with data from the east coast of England.
    Marine Pollution Bulletin. 01/1979;
  • J.C Duinker, M.T.J Hillebrand
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    ABSTRACT: Organochlorines (pentachlorobenzene, hexachlorobenzene, PCB, α-HCH, γ-HCH, β-HCH, dieldrin, endrin, p,p′-DDD) have been quantitated in water, seston, bottom sediment and interstitial water in samples from the fresh water and estuarine region of the Rhine-Meuse system obtained in 1974, 1976 and 1979.In the estuarine region, the amounts in solution are smaller than in suspension for pentachlorobenzen, hexachlorobenzene and PCB, dissolved concentrations dominating for the hexachlorocyclohexane isomers. In river water, PCB is roughly equally distributed over dissolved and suspended forms while pentachlorobenzene, hexachlorobenzene and the HCHs dominate in solution. Dissolved dieldrin, endrin and p,p′-DDD were below the limits of detection in most river water samples. However dissolved dieldrin and endrin are produced in the upper part of the estuary resulting from local pollution. During estuarine mixing, dissolved concentrations of all compounds were found to be linearly related to salinity (1974 data).Concentration data in seston and sediment in the estuarine region can be explained in terms of mixing of fluviatile and marine derived particles. It is suggested that in particular PCBs are associated specifically with finer particles.Dissolved concentrations in the central part of the Southern Bight are at the very lower end of the range of values reported for various coastal and open ocean areas. Concentrations detected in large volume samples are: penta- and hexachlorobenzene 0.1 ng·1−1; PCB (Aroclor 1254) 0.7 ng·1−1; α-HCH 0.9 ng·1−1; γ-HCH 1.0 ng·1−1; β-HCH 0.04 ng·1−1; dieldrin 0.1 ng·1−1 and endrin and p,p′-DDD < 0.01 ng·1−1.Temperature programmed GLC techniques demonstrate the contribution of lower chlorinated PCB components in the central part of the Bight. This has not been observed in other reports. Adoption of a PCB formulation with a lower degree of chlorination than the usual Aroclor 1254 as the standard for quantitation results in a significant shift of the PCB concentrations from 0.7 (Aroclor 1254 or the equivalent Clophen A50) to 4.1 ng·1−1 (Clophen A30). It is suggested that the lower chlorinated fraction is derived from atmospheric input. River water could not be excluded as a source however.Concentrations in the coastal area are higher than in the central part of the Southern Bight. Analyses of large volume water samples in 1979 are consistent with continuing conservative behaviour in the coastal area. A large fraction of the organochlorine load of the Dutch Wadden Sea is derived from the Rhine-Meuse estuary.
    Netherlands Journal of Sea Research. 01/1979;
  • J.C. Duinker, M.Th.J. Hillebrand
    Journal of Chromatography A. 03/1978; 150(1):195–199.
  • J. C. Duinker, M. Th. J. Hillebrand
    Journal of Chromatography A - J CHROMATOGR A. 01/1978; 150(1):195-199.