M.Th.J. Hillebrand

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

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Publications (20)42.38 Total impact

  • Marine Environmental Research 07/1998; 46(1):533-534. DOI:10.1016/S0141-1136(98)00089-0 · 2.76 Impact Factor
  • J.M. Everaarts · P.J. Den Besten · M.Th.J. Hillebrand · R.S. Halbrook · L.R. Shugart ·
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    ABSTRACT: Seastars (Asterias rubens L.) were collecte d at sampling locations in different areas along transects radiating into the southern North Sea, representing areas impacted by contaminants to different degrees. Strand breakage in DNA isolated from tissue of the pyloric caeca was measured by the alkaline unwinding assay, modified to allow for the isolation of highly intact DNA. The interpretation of the results is based on the incidence of DNA strand breaks (expressed as the double:total DNA ratio or F value, indicating the degree of double-strandedness). The cytochrome P-450 concentration and the benzo [a] pyrene (BaP) hydroxylase activity were measured in microsomal fractions of the pyloric caeca. The chlorinated biphenyl (CB) congeners in tissue samples from the digestive gland were determined by temperature-programmed gas-chromatography, with a CPSil8 capillary column as the stationary phase, hydrogen as the carrier gas and 63Ni-electron capture detection. Areas where seastars showed different DNA integrity could be described. The highest integrity (0.75 < f="">< 0.85)="" was="" found="" in="" the="" off-shore="" reference="" sites="" of="" the="" dogger="" bank="" and="" southern="" bight.="" the="" mean="" f="" value="" in="" seastars="" from="" most="" sampling="" locations="" varied="" between="" 55="" and="" 75%.="" the="" lowest="" dna="" integrity="" (0.35="">< f="">< 0.55)="" was="" found="" in="" specimens="" obtained="" from="" sampling="" locations="" near="" the="" river="" rhine="" delta,="" along="" the="" dutch="" coast="" and="" at="" two="" expected="" uncontaminated="" offshore="" areas.="" the="" bap="" hydroxylase="" activity="" was="" relatively="" high="" near="" the="" mouth="" of="" the="" rivers="" rhine="" and="" scheldt,="" but="" also="" at="" a="" supposedly="" clean="" site="" near="" dogger="" bank.="" the="" concentration="" of="" cb="" congeners="" in="" the="" pyloric="" caeca="" of="" seastars="" decreased="" along="" transects="" radiating="" into="" the="" southern="" north="" sea="" from="" the="" coastal="" areas="" of="" the="" netherlands;="" the="" highest="" concentrations="" were="" in="" the="" nearby="" coastal="" areas="" and="" the="" lowest="" were="" in="" the="" open="" sea="" sampling="" locations.="" the="" data="" indicate="" that="" there="" might="" be="" a="" relationship="" between="" pollution="" from="" the="" rivers="" rhine,="" meuse="" and="" scheldt="" and="" the="" incidence="" of="" dna="" strand="" breaks="" and/or="" bap="" hydroxylase="">
    Ecotoxicology 01/1998; 7(2):69-79. DOI:10.1023/A:1008811802432 · 2.71 Impact Factor
  • J.M. Everaarts · R. Heesters · C.V. Fischer · M.Th.J. Hillebrand ·

    Marine Pollution Bulletin 09/1993; 26(9):515–521. DOI:10.1016/0025-326X(93)90470-5 · 2.99 Impact Factor
  • J.P. Boon · J.M. Everaarts · M.T.J. Hillebrand · M.L. Eggens · J Pijnenburg · A Goksøyr ·
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    ABSTRACT: Female plaice (Pleuronectes platessa) were orally dosed with a gelatin capsule containing a solution of the technical PCB mixture Clophen A40 in sunflower oil. They were compared to plaice injected with a gelatin capsule containing only the sunflower oil at 10 and 16 days after injection. Even at 16 days after injection, the increase in concentrations of individual CB congeners in muscle was proportional to their contribution in Clophen A40. Biochemical effects are related to increases in concentrations of well-separable CB congeners in muscle, which increased by factors between 1.6 and 64 compared to the reference group of fish. Of both sampling points, total cytochrome P-450 levels were higher than the control groups, but surprisingly ethoxyresorufin-O-deethylase (EROD) activities did not differ between the groups. Enzyme-linked immunosorbent assay (ELISA) showed increased concentrations of the inducible cytochrome P-450IA1 in PCB-treated fish. The apparent lack of EROD induction may be due to competitive substrate inhibition by certain CB congeners present in the sample. The activity of glutathione-S-transferase (GST) (with CDNB as model substrate) was significantly elevated by PCB-treatment at day 16, but not at day 10. A longer time interval between injection with PCBs and induction of GST compared to P-450 monooxygenase activities has been reported earlier and may indicate that in fish both groups of enzymes are regulated individually and not as an [Arylhydrocarbon] gene battery as appears to be the case in mammals. Haemoglobin concentrations and MCHC were decreased in fish treated with Clophen A40. Haematocrit values did not differ between groups of fish.
    Science of The Total Environment 05/1992; 114:113-33. DOI:10.1016/0048-9697(92)90418-R · 4.10 Impact Factor
  • J.M. Everaarts · A De Buck · M.Th.J. Hillebrand · J.P. Boon ·
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    ABSTRACT: Polychlorinated biphenyl concentrations in brain and liver oystercatchers, Haematopus ostralegis, increased similarly in males and females until sexual maturation. The concentrations were higher in adult males than in subadults, but for females the concentrations were lower in adults than in subadults. Absolute PCB, dieldrin and DDE concentrations were higher in liver than in brain. Compared with these compounds, alpha-HCH was relatively enriched in brain. No significant relation between pesticide concentrations and age or sex could be established. Despite differences in absolute PCB concentrations, the PCB patterns were very similar between all categories of birds and between brain and liver of the same animals. Only in the brain of juvenile males were some congeners present in relatively higher concentrations than in the brain of subadults and adults. Oystercatchers are able to metabolize CB congeners with vicinal H-atoms in the meta and para positions irrespective of the number of ortho-chlorines present. However, their ability to metabolize congeners with vicinal H-atoms in the ortho and meta positions is limited.
    Science of The Total Environment 04/1991; 100 Spec No:483-99. DOI:10.1016/0048-9697(91)90389-V · 4.10 Impact Factor
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    ABSTRACT: Polychlorinated biphenyls (PCBs), organochlorine pesticides and their persistent metabolites were identified in epibenthic animals from the estuaries of the rivers Brantas and Solo and from Strait Madura, Strait Bali and the Java Sea in July and November 1984.Samples of different phyla showed similar general geographical trends for the compounds investigated. Contamination with p,p′-DDE was of major importance in the river Porong, a distributary of the Brantas river system. Increased concentrations of PCBs were found near Surabaya.In Strait Madura, p,p′-DDE and PCBs were increased only in animals from the western part. Therefore the dispersion of the contaminants in biota appeared to be determined by the residual currents caused by the SE trade winds prevailing in both periods of sampling (July and November 1984).Generally no differences existed between the two sampling periods, except in the Java Sea, where PCBs were only detected during the November cruise. Compared to the animals from Strait Madura, the PCB patterns showed increased contributions of tri- and tetrachlorobiphenyls. This could not be related to differences in PCB-patterns of water or suspended particles.The compounds QCB, HCB, α-HCH, ß-HCH, o,p′-DDD, methoxychlor and several cyclodienes were generally below detection limits.
    Netherlands Journal of Sea Research 08/1989; 23(4-23):427-440. DOI:10.1016/0077-7579(89)90026-4
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    J.C. Duinker · A.H. Knap · K.C. Binkley · G.H. Van Dam · A. Darrel-Rew · M.T.J. Hillebrand ·
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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 02/1988; 19(2-19):74-79. DOI:10.1016/0025-326X(88)90785-0 · 2.99 Impact Factor
  • 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. DOI:10.1016/0165-9936(87)87027-9 · 6.47 Impact Factor
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    E.K. Duursma · J. Nieuwenhuize · J.M. Van Liere · M.T.J. Hillebrand ·
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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 08/1986; 20(2-3-20):239-251. DOI:10.1016/0077-7579(86)90046-3
  • J.C. Duinker · M.T.J. Hillebrand · R.F. Nolting · S. Wellershaus · N. Kingo Jacobsen ·
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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; 14(3-4-14):237-267. DOI:10.1016/0077-7579(80)90002-2
  • 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 10/1983; 17(1-17):19-38. DOI:10.1016/0077-7579(83)90003-0
  • J C Duinker · M. T. J. 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. DOI:10.1021/es00114a003 · 5.33 Impact Factor
  • J C Duinker · M. T. J. 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. DOI:10.1007/BF01608762 · 1.26 Impact Factor
  • J.C. Duinker · M.T.J. Hillebrand · R.F. Nolting · S WELLERSHAUS ·
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    ABSTRACT: In summer 1976, measurements were made of metals and organochlorines in solution and in suspension along with studies of transport and mixing of water and particulates in the freshwater and estuarine region of the river Ems during typical neap tide conditions. During our observations a fluid mud layer occurred on the bottom. We observed some particular properties: the mean grain size was greater than in other samples, and the organic carbon content in seston was high and consequently dissolved oxygen concentrations in water were low. There was no difference in HCH contents between fluid mud-seston and other samples. Mn content in this seston was high, and its leacheable portion was the greatest in all samples. The behaviour of other metals was different: contents were lower and thier leacheable portions were also lower than in other samples. Concentrations of Cu, Zn, and Cd in solution in the mixing zone were higher than in the fresh water and marine end members, probably as a result of local land-based sources. Variations in mineral composition of suspended material in the longitudinal profile (S = 0 to 30.10-3 were minor. Variations in metal contents of suspended matter were interpreted in terms of variations in size/density properties. A wide range of PCB components was present in solution and suspension at concentrations in the pico- to nanogram per dm3 range.
    Netherlands Journal of Sea Research 07/1982; 15(2):141-169. DOI:10.1016/0077-7579(82)90002-3
  • G EDER · W ERNST · H GOERKE · J.C. Duinker · M.T.J. 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 10/1981; 15(1):78-87. DOI:10.1016/0077-7579(81)90007-7
  • J C Duinker · M. T. J. Hillebrand · K H Palmork · S Wilhelmsen ·

    Bulletin of Environmental Contamination and Toxicology 01/1981; 25(6):956-64. DOI:10.1007/BF01985638 · 1.26 Impact Factor
  • J C Duinker · M. Th. J. 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. DOI:10.1007/BF01770032 · 1.26 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 12/1979; 10(12-10):360-364. DOI:10.1016/0025-326X(79)90380-1 · 2.99 Impact Factor
  • 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 11/1979; 13(2-13):256-281. DOI:10.1016/0077-7579(79)90006-1
  • J.C. Duinker · M.Th.J. Hillebrand ·

    Journal of Chromatography A 03/1978; 150(1):195–199. DOI:10.1016/S0021-9673(01)92112-0 · 4.17 Impact Factor