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Jacob de Boer

Publications and source records attributed to Jacob de Boer.

14 recordsLinked to original sources

Feasibility of gamma irradiation as a stabilisation technique in the preparation of tissue reference materials for a range of shellfish toxins.

The effect of gamma-irradiation on concentrations of hydrophilic and lipophilic phycotoxins has been investigated by use of HPLC-UV and LC-MS. Pure toxins in organic solvents and toxins in mussel (Mytilus edulis) tissues were irradiated at three different doses. In solution all toxin concentrations were reduced to some extent. Most severe decreases were observed for domoic acid and yessotoxin, for which the smallest dose of irradiation led to almost complete destruction. For pectenotoxin-2 the decrease in concentration was less severe but still continuous with increasing dose. Azaspiracid-1 and okadaic acid were the least affected in solution. In shellfish tissue the decrease in toxin concentrations was much reduced compared with the effect in solution. After irradiation at the highest dose reductions in concentrations were between ca. 5 and 20% for the lipophilic toxins and there was no statistical difference between control and irradiated samples for azaspiracids in tissue. Irradiation of shellfish tissues contaminated with domoic acid led to a more continuous decrease in the amount of the toxin with increasing dose. The effect of irradiation on the viability of microbial activity in shellfish tissues was assessed by using total viable counting techniques. Microbial activity depended on the type of shellfish and on the pretreatment of the shellfish tissues (with or without heat treatment). As far as we are aware this is the first investigation of the effectiveness of irradiation as a technique for stabilising tissue reference materials for determination of phycotoxins. Our results suggest that this technique is not effective for materials containing domoic acid. It does, however, merit further investigation as a stabilisation procedure for preparation of shellfish tissue materials for some lipophilic toxins, in particular azaspiracids. Chemical structures of the toxins investigated in the study.

Animals↗

Levels and trends of brominated flame retardants in the European environment.

In this paper, we review those data which have recently become available for brominated flame retardants (particularly the brominated diphenyl ethers (BDEs) and hexabromocyclododecane (HBCD)) in samples from the European environment. Environmental compartments studied comprise the atmosphere, sediments and soils, sewage sludges, and a variety of biological samples and food chains. This is currently a very active research area, and we cite over 70 studies reported in the literature during 2003-04. Findings include that the input of BDEs (especially BDE209) to the Baltic Sea by atmospheric deposition now exceeds that of PCBs by a factor of almost 40 times. Sewage sludge samples from both industrial and background locations show concentrations of BDEs, HBCD and tetrabromobisphenol-A (TBBP-A) that are of a similar order, indicating that the major source is from diffuse leaching from products into wastewater streams from users, households and industries generally. Point-sources from industries using BFRs (e.g. the textile industry) also generate local hot-spots. Sediment core studies identified the presence of two of the three PBDE formulations. The penta-mix formulation was clearly present from the beginning of the 1970s, but the deca-mix only appeared in the late 1970s. BDE183, BDE209 and HBCD were detected in peregrine falcons from Sweden and other birds feeding on terrestrial food chains. BDEs are found widely distributed in fish, including those from high mountain lakes in Europe, as a consequence of long-range atmospheric transport and deposition. A temporal trend study in archived freeze-dried mussels from the Seine estuary, France, indicated an exponential increase in BDE concentrations during the period 1982-1993, which levelled off in 1999 and 2001 and then began to decline after 2002. HBCD was detected in liver and blubber samples from harbour seals and harbour porpoises from the Wadden and North Seas, though very few animals yielded positive values for TBBP-A. There are difficulties in comparing data on summation operatorBDE from studies in which different suites of BDE congeners have been determined, and we suggest a common suite which will allow the study of all three commercial PBDE formulations.

Air↗

Retention-time database of 126 polybrominated diphenyl ether congeners and two bromkal technical mixtures on seven capillary gas chromatographic columns.

The elution order of 126 polybrominated diphenyl ethers (PBDE) was determined for seven different gas chromatographic (GC) stationary phases. The resulting database facilitates selection of the most suitable GC columns for developing a quantitative, congener-specific BDE analysis and the testing of retention prediction algorithms based on structure relationships of GC phases and congener substitution patterns. In addition, co-elutions of the principal BDE congeners with other BDEs and/or with other brominated flame retardants were investigated and, as an application, the composition of two Bromkal mixtures (70-5DE and 79-8DE) was studied.

Algorithms↗

Enantiomeric separation of chiral polychlorinated biphenyls on beta-cyclodextrin capillary columns by means of heart-cut multidimensional gas chromatography and comprehensive two-dimensional gas chromatography. Application to food samples.

Three commercially available chiral capillary columns, Chirasil-Dex, BGB-176SE, and BGB-172, have been evaluated for the separation into enantiomers of the 19 chiral polychlorinated biphenyls (PCB) congeners stable at room temperature. The enantiomers of 15 chiral PCBs were, at least to some extent, separated using these beta-cyclodextrin based columns. Multidimensional techniques, such as heart-cut multi-dimensional gas chromatography (heart-cut MDGC) and comprehensive two-dimensional gas chromatography (GC x GC), were investigated for their ability to solve coelution problems with other PCBs present in commercial mixtures and real-life samples. Heart-cut MDGC improved the separation as compared to one-dimensional GC, and enantiomeric fractions of the investigated chiral PCBs could be determined free from interferences. However, limitations on the number of target compounds that can be transferred to the second column in a single run and, therefore, the time consumption, have led to the evaluation of GC x GC as an alternative for this type of analysis. With GC x GC, two column set-ups were tested, both having a chiral column as first-dimension column, and two different polar stationary phase columns in the second dimension. On using both column combinations, congeners 84, 91, 95, 132, 135, 136, 149, 174, and 176 could be determined free from coelutions with other PCBs. Results on the application of heart-cut MDGC to food samples such as milk and cheese are given, as well as the first results on the application of GC x GC to this type of samples.

Animals↗

An integrated assessment of estrogenic contamination and biological effects in the aquatic environment of The Netherlands.

An extensive study was carried out in the Netherlands on the occurrence of a number of estrogenic compounds in surface water, sediment, biota, wastewater, rainwater and on the associated effects in fish. Compounds investigated included natural and synthetic hormones, phthalates, alkylphenol(ethoxylate)s and bisphenol-A. The results showed that almost all selected (xeno-)estrogens were present at low concentrations in the aquatic environment. Locally, they were found at higher levels. Hormones and nonylphenol(ethoxylate)s were present in concentrations that are reportedly high enough to cause estrogenic effects in fish. Field surveys did not disclose significant estrogenic effects in male flounder (Platichthys flesus) in the open sea and in Dutch estuaries. Minor to moderate estrogenic effects were observed in bream (Abramis brama) in major inland surface waters such as lowland rivers and a harbor area. The prevalence of feminizing effects in male fish is largest in small regional surface waters that are strongly influenced by sources of potential hormone-disrupting compounds. High concentrations of plasma vitellogenin and an increased prevalence of ovotestes occurred in wild male bream in a small river receiving a considerable load of effluent from a large sewage treatment plant. After employing in vitro and in vivo bioassays, both in situ and in the laboratory, we conclude that in this case hormones (especially 17 alpha-ethynylestradiol) and possibly also nonylphenol(ethoxylate)s are primarily responsible for these effects.

Animals↗

Heparin normalizes allergen-induced nitric oxide deficiency and airway hyperresponsiveness.

It has been established that polycations cause airway hyperresponsiveness (AHR) to methacholine by inducing a deficiency of constitutive nitric oxide synthase (cNOS)-derived bronchodilating nitric oxide (NO). Since a deficiency of cNOS-derived NO also contributes to allergen-induced AHR after the early asthmatic reaction (EAR) and since this AHR is associated with the release of polycationic proteins from infiltrated eosinophils in the airways, we hypothesized that endogenous polycations underlie or at least contribute to the allergen-induced NO deficiency and AHR. Using a guinea-pig model of allergic asthma, we addressed this hypothesis by examining the effect of the polyanion heparin, acting as a polycation antagonist, on the responsiveness to methacholine of isolated perfused tracheae from unchallenged control animals and from animals 6 h after ovalbumin challenge, that is, after the EAR. A 2.0-fold AHR (P<0.001) to intraluminal administration of methacholine was observed in airways from allergen-challenged animals compared to control. Incubation of these airways with 250 U ml(-1) heparin completely normalized the observed hyperresponsiveness (P<0.001), whereas the responsiveness to methacholine of airways from unchallenged control animals was not affected. The effect of heparin on airways from allergen-challenged guinea-pigs was dose-dependently (0.1 and 1.0 mM) reversed by the NOS inhibitor L-NAME (P<0.01). These results indicate that endogenous (presumably eosinophil-derived) polycations are involved in allergen-induced NO deficiency and AHR after the EAR, probably by inhibition of l-arginine transport.

Allergens↗

Levels of polybrominated diphenyl ether flame retardants in sediment cores from Western Europe.

The levels of 14 brominated diphenyl ether (BDE)-congeners in sediment cores from three locations in Western Europe have been determined by GC/MS (negative chemical ionization mode). Sediments from the Drammenfjord (Norway), the western Wadden Sea (The Netherlands), and the freshwater Lake Woserin (Mecklenburg-Vorpommern, Germany) showed a time-dependent pattern in the distribution of BDEs since the beginning of the industrial production of polybrominated diphenyl ether (PBDE) formulations. Two out of three commercially available PBDE formulations could be distinguished. Starting from the beginning of the 1970s, the penta-mix formulation is clearly present, but the deca-mix formulation is only present since the late 1970s. The octa-mix formulation appeared to be still absent in these sediments, as its marker-congener, BDE183, was never detected. In the cores from the western Wadden Sea and Lake Woserin, all TOC-normalized concentrations of the penta-BDE-derived congeners were leveling off in the most recent sediment layers representing 1995 and 1997, whereas those in the Drammenfjord were still increasing in 1999. The levels of BDE209, however, decreased in the most recent layer of all three cores. In Lake Woserin, the concentrations of BDE209 were much less elevated above those of the tri- to hexa-BDEs than in the other the two areas. This might be due to the absence of a significant PBDE input from sources other than the atmosphere to this rural lake. The absence of all PBDE congeners in the older layers of the three sediment cores, as well as in several 100-150-My-old layers from an extremely organic-rich marine sediment from the Kimmeridge clay formation in Dorset (UK), indicated the absence of natural production of the BDE congeners analyzed.

Environmental Monitoring↗

Developments in the use of chromatographic techniques in marine laboratories for the determination of halogenated contaminants and polycyclic aromatic hydrocarbons.

Chromatography has been an important tool in marine laboratories. Since the 1960s, marine laboratories have been involved in the analysis of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs), and brominated flame retardants (BFRs). Column chromatography and liquid chromatography (LC) techniques have been used, mainly in the clean-up phase, while gas chromatography (GC) has been used extensively in the final determination of these contaminants. Developments have been observed from the use of packed GC columns, via capillary columns to the use of heart-cut multi-dimensional GC and comprehensive multi-dimensional GC. The progress made in interlaboratory studies and the availability of certified reference materials are discussed.

Chromatography, Gas↗

Determination of brominated flame retardants, with emphasis on polybrominated diphenyl ethers (PBDEs) in environmental and human samples--a review.

Analytical methods for the determination of brominated flame retardants (BFRs), with a special emphasis on polybrominated diphenyl ethers (PBDEs) are reviewed. A number of procedures, which can be applied to the analysis of PBDEs and polybrominated biphenyls (PBBs), and in some cases for hexabromocyclododecane (HBCD), in environmental and human samples are described. Because several BFRs, such as tetrabromobisphenol-A (TBBP-A), BDE 209 and, to some extent, HBCD, may require a different approach, specific advice on their analysis is given separately when needed. Sample pretreatment, extraction, cleanup and fractionation, injection techniques, chromatographic separation, detection methods, quality control and method validation are discussed. For each topic, an overview is given of the current status of the field and recommendations for an appropriate analytical approach are presented.

Chemical Fractionation↗

Polybrominated diphenyl ethers in influents, suspended particulate matter, sediments, sewage treatment plant and effluents and biota from the Netherlands.

Polybrominated diphenyl ethers (PBDEs) have been determined in 133 samples of suspended particulate matter (SPM), sediments, sewage treatment plant (STP) influents and effluents, fish and mussels from various locations in The Netherlands, as a part of a large Dutch national study on estrogenic contaminants in the aquatic environment (LOES project). Some PBBs were also analysed but not found in any of the samples at detectable levels. PBDEs and PBBs were included in this study because indications of long term effects on the balance of endocrine systems were found in the literature. High concentrations of decaBDE (up to 4600 g/kg dry weight) were found in SPM from the Western Scheldt. These levels are possibly related to spillage during use of PBDEs in industries upstream the river Scheldt in Belgium. SPM was identified as an important carrier for higher brominated diphenyl ethers in the aquatic environment. DecaBDE was not found at detectable levels in flounder, bream and mussels. The bioaccumulation of decaBDE in these fish and shellfish samples is apparently limited. Lower brominated PBDE congeners (tetra/penta) were also found in the Western Scheldt as well as in the Rhine delta and the river Meuse, but in much lower concentrations than the decaBDE. In contrast with decaBDE, the tetra and pentaBDEs were found in biota. It was concluded that at least a small part of the PBDE can pass STPs.

Animals↗

Preliminary study on the occurrence of brominated organic compounds in Dutch marine organisms.

The extracts of three marine organisms; the ascidian Ciona intestinalis, the brown seaweed Sargassum muticum and the sponge Halichondria panicea, all elicited a number of brominated compounds, some of which were tentatively identified. Tribromophenol was observed in all species. This compound, also industrially produced as flame retardant and fungicide, was likely due to endogenous production.

Animals↗

Distribution of organobrominated and organochlorinated contaminants in Belgian human adipose tissue.

We have measured the levels of flame retardants, polybrominated diphenyl ethers (PBDEs), in 20 recent human adipose tissues from Belgium and compared them to other organohalogen compounds such as polychlorinated biphenyls (PCBs), hexachlorobenzene, 2,2-bis(4-chlorophenyl)-1,1,1-trichloroethane (p,p'-DDT), and its metabolite, 2,2-bis(4-chlorophenyl)-1,1-dichloroethylene (p,p'-DDE). After Soxhlet extraction and cleanup on acidified silica solid-phase extraction cartridges, analysis was achieved by capillary gas chromatography/electron impact mass spectrometry. The method allowed the determination of 5 PBDE and 35 PCB congeners. Concentrations of PBDEs (sum of congeners IUPAC Nos. 28, 47, 99, 100, and 153) ranged between 2.2 and 11.7 ng/g lipid weight and were on the lower end of reported PBDE concentrations in European countries. The median value for the sum of PCBs (35 congeners) was 841 ng/g lipid weight and ranged from 286 to 1802 ng/g lipid weight. The median value for the sum of DDTs (calculated from p,p'-DDE and p,p'-DDT) was 290 ng/g lipid weight and ranged from 47 to 2802 ng/g lipid weight. The sum of PCBs showed a good correlation with the sum of DDTs (r=0.77, P<0.05), while the correlation with the sum of PBDEs was weaker (r=0.56, P<0.05). No age dependency was found for PBDEs (r=0.09), while PCBs and DDTs showed higher correlation coefficients with age (r=0.59 and 0.40, respectively, P<0.05).

Adipose Tissue↗

First world-wide interlaboratory study on polybrominated diphenylethers (PBDEs).

The first world-wide interlaboratory study on PBDEs, organised between November 1999 and April 2000, involved five biological samples, two sediments and two standard solutions. These materials were sent to 26 participants in nine different countries. Results were returned from 18 laboratories. The results reported for BDE 47 were acceptable with a range of relative standard deviations (Rsd) of 17-40%. Results for the BDEs 99 (Rsd 25-77%), BDE 100 (Rsd 19-48%), 153 (Rsd 30-48%) and 154 (Rsd 25-43%) showed that a further improvement of these analyses is needed. The BDE 209 analysis is not under the control of the participating laboratories. The data reported for the biota samples were very variable and for the two sediments Rsd values of 48% and 78% were obtained. It is recommended that analysts pay more attention to the special requirements for the BDE 209 analysis such as avoiding exposure to intensive light and exposure for too long times to too high temperatures.

Environmental Monitoring↗

Comparative tests to improve the gas chromatographic analysis of chlorobornanes in fish samples.

A comparison was made between electron capture negative ionization quadrupole mass spectrometry (ECNI-MS) and electron capture detection (ECD) with regard to repeatability and reproducibility for the gas chromatographic (GC) analysis of toxaphene congeners [chlorobornanes (CHBs)]. The tests, including standard solutions and several cleaned fish extracts, showed larger relative standard deviations (RSDs) for the repeatability of ECNI-MS but no differences in the reproducibility of the 2 techniques. The sensitivity of the GC-ECNI-MS was considerably better than that of GC/ECD. Four stepwise-designed comparative tests were also conducted on GC analysis, cleanup, and the complete method. The results showed that, according to the current state-of-the-art, coefficients of variation for the between-laboratory performance were not < 20% and were usually between 20 and 30%. In spite of separation problems, e.g., for CHB 26, which cannot be separated into a single-component peak, a 95% methyl 5% phenyl polysiloxane (CP Sil 8) column was preferred to more polar columns for the analysis of CHBs 26, 40, 41, 44, 50, and 62. CHB 62 was more difficult to determine than CHB 26 and 50. Addition of the CHBs 40, 41, and 44 to the standard set of 3 chlorobornanes (26, 50, and 62) resulted in more separation problems. A 3-step cleanup method was recommended.

Animals↗