Biomedical subjects

Peter Haglund

Publications and source records attributed to Peter Haglund.

7 recordsLinked to original sources

PubMed2003

A review of environmental toxicant analysis by using multidimensional gas chromatography and comprehensive GC.

The purpose of this review is to highlight the developments in coupled-column gas chromatography methods for qualitative analysis of selected environmental toxicants such as dioxin, polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), etc. In particular, the new technique of GC x GC will be introduced, and its role, and the promise it offers to this field is discussed. The benefits of enhanced separation to quantitative analysis will be considered. In order to perform an accurate risk assessment, both the dose and biological effects of environmental toxicants have to be determined with a high degree of certainty. This is most often achieved by using chromatographic methods. Given the complexity of most environmental sample extracts, single-column gas chromatography is unable to fully resolve all the components of interest frequently leading to a positive bias in the reported concentrations. Advanced separation tools, such as multidimensional gas chromatography (MDGC), were investigated quite early and demonstrated improvements in separation. However, limitations in the number of target analytes that could be analyzed in a single run as well as insufficient robustness lead to a continued interest in alternative solutions. The parallel development of mass spectrometric identification and quantification strategies proved useful in many cases, although it frequently failed to provide positive identification of chromatographically unresolved isomeric compounds. More recently, comprehensive two-dimensional gas chromatography (GC x GC) may offer a solution to that problem, especially because it offers enhanced resolution for complex mixtures containing trace level environmental toxicants.

Chromatography, Gas↗

PubMed2003

Degradation and formation of polycyclic aromatic compounds during bioslurry treatment of an aged gasworks soil.

The goals of this study were to investigate the relative degradation rates of polycyclic aromatic compounds (PACs) in contaminated soil, and to assess whether persistent oxidation products are formed during their degradation. Samples were taken on five occasions during a pilot-scale bioslurry treatment of soil from a former gasworks site. More than 100 PACs were identified in the soil, including unsubstituted polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs (alkyl-PAHs), heterocyclic PACs, and oxygenated PAHs (oxy-PAHs), such as ketones, quinones, and coumarins. During the treatment, the low molecular weight PAHs and heterocyclics were degraded faster than the high molecular weight compounds. The unsubstituted PAHs also appear to have degraded more quickly than the corresponding alkyl-PAHs and nitrogen-containing heterocyclics. No new oxidation products that were not present in the untreated soil were identified after the soil treatment. However, oxy-PAHs that were present in the untreated soil were generally degraded more slowly than the parent compounds, suggesting that they were formed during the treatment or that they are more persistent. Two oxidation products, 1-acenaphthenone and 4-oxapyrene-5-one, were found at significantly higher concentrations at the end of the study. Because oxy-PAHs can be acutely toxic, mutagenic, or carcinogenic, we suggest that this group of compounds should also be monitored during the treatment of PAH-contaminated soil.

Biodegradation, Environmental↗

PubMed2002

Effects of temperature and flow regulated carbon dioxide cooling in longitudinally modulated cryogenic systems for comprehensive two-dimensional gas chromatography.

Two different modes of temperature regulation in longitudinally modulated cryogenic systems (LMCSs) for comprehensive two-dimensional gas chromatography (GC x GC) were compared. Carbon dioxide was used as coolant. In the first mode of operation, the temperature of the trap was regulated to pre-set temperature using a digital temperature controller ("the constant temperature mode"). In the second, the temperature was regulated to a fixed negative offset to the oven temperature by using a constant flow of CO2 ("the constant flow mode"). A number of problems were occasionally observed using the constant temperature mode: (1) severe band broadening of high boiling analytes in the second dimension; (2) non-Gaussian reconstructed first-dimension peak profiles; (3) high background due to modulation of first-dimension column bleed. It was concluded that these problems were associated with inefficient solute remobilization at low LMCS trap temperatures (1 and 2) or large trap temperature fluctuations (3). These problems could be avoided or significantly reduced by using the constant flow mode. Best results were obtained as the trap temperature was kept about 70 degrees C below the oven temperature.

Carbon Dioxide↗

PubMed2002

Influence of chromatographic conditions on separation in comprehensive gas chromatography.

Comprehensive gas chromatography (GC x GC) is now established as a powerful technique, which offers unprecedented separation power. For complex samples, the distribution of peaks in the two-dimensional (2D) space still may need to be optimised. Since temperature (T) is a critical variable, and compounds can be shifted in relative positions on column 1 arising from temperature program rate (rT) changes, and since retention in the second dimension, D2 (2tR) is likewise affected by the prevailing T (elution temperature; Te), then any factors which alter Te will affect the extent of separation in D2. Since temperature program and carrier gas velocity rate will affect the Te of the solutes, these two factors are considered in this paper. Apart from these two parameters, results of different stationary phase choice for the second dimension column as well as the second dimension column length are reported. rT is found to have the most profound impact on the Te of solutes and will be more likely to cause an inversion of elution order if such behaviour can occur. Peak widths and 2tR increase with a decrease in Te. On the other hand, flow-rate has less impact on peak widths and 2tR although Te is affected by a change in flow-rate. Specific solute-stationary phase interactions will cause the elution order of certain solutes to be altered, and may be observed when a different stationary phase is employed as the second column, depending on the solute-stationary phase separation mechanism. Experiments conducted on different second dimension column length showed that although a longer column will lead to better separations, wrap-around may confound the separation process and may cause the solutes from sequential modulation events to co-elute. Thus a suitable second dimension column phase and length must be employed in order to obtain good separation. The factors investigated in this study will cause different extents of changes in the solute elution order and solute separations, and will affect the 2D contour presentation.

Chromatography, Gas↗

PubMed2002

Multivariate physicochemical characterisation and quantitative structure-property relationship modelling of polybrominated diphenyl ethers.

Levels of polybrominated diphenyl ethers (PBDEs) are increasing in the environment and may cause long-term environmental problems. Developing a model describing the chemical variation among the 209 possible congeners would be a useful step in any systematic approach for assessing the fate and risk posed by the PBDEs. Therefore, 40 physicochemical descriptors were derived for all PBDEs using a semi-empirical method (AM1), molecular mechanics, and empirically estimated parameters. Descriptors included heats of formation, frontier molecular orbital energies, atomic charges, dipole moments, logP values, and molecular surface areas. Principal component analysis (PCA) was used to evaluate the descriptors. The first four PCs, explaining 76% of the variation in the data, described the size, charge distribution and symmetric elements of the congeners. A quantitative structure-activity relationship model was constructed based on data for dioxin-like activity (using the luciferase bioassay) for 17 PBDEs with the partial least squares method. In addition, quantitative structure-property relationship models for gas chromatographic relative retention times on four capillary columns were developed. These models proved suitable to assist in the identification of untested PBDEs. Based on the results of the PCA, a factorial design was applied for selecting 21 representative congeners. PBDEs 11, 13, 17, 32, 35, 47, 53, 77, 85, 99, 119, 135, 153, 155, 156, 169, 176, 181, 190, 192, and 209. The spacing of these congeners in the physicochemical domain maximises the coverage of key factors such as molecular size and substitution pattern. Consideration of the selected congeners should be useful for guiding the synthesis of new compounds for use in future studies of the fate and biological effects of PBDEs.

Biological Assay↗

PubMed2002

Subchronic toxicity of Baltic herring oil and its fractions in the rat I: Fractionation and levels of organohalogen pollutants.

Baltic herring (Clupea harengus) oil was extracted and fractionated. To examine the contribution to toxicity and biological effects of different halogenated organic pollutants, the herring oil and the fractions were mixed into pelleted food and given to Sprague-Dawley female rats at three levels, corresponding to a human intake of 1.6, 8.2 and 34.4 kg fish per week. Herring oil, its fractions, as well as liver tissues from exposed rats, were analyzed for: eight chlorinated biphenyls, all 2,3,7,8-substituted chlorinated dibenzo-p-dioxins and dibenzofurans, hexachlorocyclohexanes, hexachlorobenzene, 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane (DDT), DDT-metabolites, three brominated diphenylethers as well as extractable organically bound chlorine and halogenated fatty acids. A bioassay (EROD) was used for measuring the dioxin-like enzyme induction activity. Nordic Sea lodda (Mallotus villosus) oil was used as a nutritionally equivalent control, with much lower levels of halogenated organic pollutants. A full toxicological subchronic examination is reported in the following paper (Stern et al. 2002). In this study, we report that the fractionation procedure resulted in a substantial reduction of most of the pollutants in the triacylglycerol fraction, and a pronounced enrichment of most of the pollutants into the two other fractions. However, all contaminants were present at some levels in all of the fractions. The concentrations of organohalogens found in this study were representative for Baltic herring during the mid-1990s. Rat liver tissue showed similar residue patterns as the diet, with the exception of chlorinated dibenzo-p-dioxin and dibenzofuran congeners that had a higher liver retention than pesticides, chlorinated biphenyls and brominated diphenylethers.

Animals↗

PubMed2002

Concentrations and enantiomer fractions of organochlorine compounds in Baltic species hit by reproductive impairment.

Concentrations and enantiomer fractions (EFs) of organochlorine compounds (OCs) were determined in tissues of gray seal (Halichoerus grypus) and salmon (Salmo salar) originating from the Baltic Sea. The selected seal specimens ranged from starved to unstarved animals, and some of them suffered from a disease complex, while the salmon samples originated from individuals, which were known to produce offspring with and without the M74 syndrome. Significant differences in residue levels and EFs were found between seal groups but not between M74 salmon and non-M74 salmon. The relations between chemical and biological variables of seal samples were investigated with multivariate statistics. Poor health status correlated strongly with age, while bad nutrition condition was associated mainly with high pollution loads and distinctively nonracemic chiral OC compositions. High biotransformation rate (as indicated by fraction of chlordane metabolites in relation to total level of chlordanes) was also associated with large deviations from racemic values and high contaminant levels.

Animals↗