Biomedical subjects

Jan H Christensen

Publications and source records attributed to Jan H Christensen.

10 recordsLinked to original sources

PubMed2005

Characterization, weathering, and application of sesquiterpanes to source identification of spilled lighter petroleum products.

Biomarkers have become increasingly important for identifying the source of spilled oil, due to their specificity and high resistance to biodegradation. The biomarkers most commonly used in forensic investigations are the high molecular weight (MW) tri- and pentacyclic terpanes and steranes. For lighter petroleum products such as jet fuels and diesels, the refining processes remove most high MW biomarkers from the original crude oil feedstock. The smaller bicyclic sesquiterpanes, however, are concentrated in these products. Sesquiterpanes are ubiquitous components of crude oils and ancient sediments. Examination of GC-MS chromatograms of these bicyclic biomarkers using their characteristic fragment ions (m/z 123, 179, 193, and 207) provides a highly diagnostic means for identifying spilled oil, particularly for lighter refined product samples that are difficult to identify by current techniques. In this work, sesquiterpanes in crude oils and petroleum products are identified and characterized, distributions of sesquiterpanes in oils and refined products are compared, the effects of evaporative weathering on sesquiterpane distributions are examined, and a methodology using diagnostic indices of sesquiterpanes is developed for oil correlation and differentiation. Finally, two case studies are presented to illustrate the unique utility of sesquiterpanes for fingerprinting and identifying unknown diesel spills.

Chromatography, Gas↗

PubMed2005

Multivariate statistical methods for evaluating biodegradation of mineral oil.

Two methods were developed for evaluating natural attenuation and bioremediation of mineral oil after environmental spills and during in vitro experiments. Gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring (SIM) mode was used to obtain compound-specific data. The chromatographic data were then preprocessed either by calculating the first derivative, retention time alignment and normalization or by peak identification, quantification and calculation of diagnostic ratios within homologue series of polycyclic aromatic compounds (PACs). Finally, principal component analysis (PCA) was applied to the preprocessed chromatograms or diagnostic ratios to study the fate of the oil. The methods were applied to data from an in vitro biodegradation experiment with a North Sea crude oil exposed to three mixtures of bacterial strains: R (alkane degraders and surfactant producers), U (PAC degraders) and M (mixture of R- and U-strains) over a 1-year-period with five sampling times. Assessment of variation in degradability within isomer groups of methylfluorenes (m/z 180), methylphenanthrenes (m/z 192) and methyldibenzothiophenes (m/z 198) was used to evaluate the effects of microbial degradation on the composition of the oil. The two evaluation methods gave comparable results. In the objective pattern matching approach, principal component 1 (PC1) described the general changes in the isomer abundances, whereas M samples were separated from U and R samples along PC2. Furthermore, in the diagnostic ratio approach, a third component (PC3) could be extracted; although minor, it separated R samples from U and M samples. These results demonstrated that the two methods were able to differentiate between the effects due to the different bacterial activities, and that bacterial strain mixtures affected the PAC isomer patterns in different ways in accordance with their different metabolic capabilities.

Bacteria↗

PubMed2005

Characterization and matching of oil samples using fluorescence spectroscopy and parallel factor analysis.

A novel approach for matching oil samples by fluorescence spectroscopy combined with three-way decomposition of spectra is presented. It offers an objective fingerprinting based on the relative composition of polycyclic aromatic compounds (PACs) in oils. The method is complementary to GC-FID for initial screening of oil samples but can also be used for prescreening in the field, onboard ships, using a portable fluorescence spectrometer. Parallel factor analysis (PARAFAC) was applied to fluorescence excitation-emission matrixes (EEMs) of heavy fuel oils (HFOs), light fuel oils, lubricating oils, crude oils, unknown oils, and a sample collected in the spill area two weeks after the Baltic Carrier oil spill (Denmark, 2001). A total of 112 EEMs were decomposed into a five-factor PARAFAC model using excitation wavelengths from 245 to 400 nm and emission wavelengths from 280 to 550 nm. The PARAFAC factors were compared to EEMs of PAC standards with two to five rings, and the comparisons indicate that each of the factors can be related to a mixture of PACs with similar fluorescence characteristics: a mixture of naphthalenes and dibenzothiophenes, fluorenes, phenanthrenes, chrysenes, and five-ring PACs, respectively. Oils were grouped in score plots according to oil type. Except for HFOs and crude oils, the method easily discriminated between the four oil types. Minor overlaps of HFOs and crude oils were observed along all five PARAFAC factors, and the variability of crude oils was large along factor 2 due to a varying content of five-ring PACs. The spill sample was correctly assigned as a HFO with similar PAC pattern as oil from the cargo tank of the Baltic Carrier by comparing the correlation coefficient of scores for the oil spill sample and possible source oils (i.e., oils in the database).

Databases, Factual↗

PubMed2005

Chromatographic preprocessing of GC-MS data for analysis of complex chemical mixtures.

Hyphenated analytical techniques such as gas chromatography-mass spectrometry (GC-MS) can provide extensive amounts of analytical data when applied to environmental samples. Quantitative analyses of complex contaminant mixtures by commercial preprocessing software are time-consuming, and baseline distortion and incomplete peak resolution increase the uncertainty and subjectivity of peak quantification. Here, we present a semi-automatic method developed specific for processing complex first-order chromatographic data (e.g. selected ion monitoring in GC-MS) prior to chemometric data analysis. Chromatograms are converted into semi-quantitative variables (e.g. diagnostic ratios (DRs)) that can be exported directly to appropriate softwares. The method is based on automatic peak matching, initial parameterization, alternating background noise reduction and peak estimation using mathematical functions (Gaussian and exponential-Gaussian hybrid) with few (i.e. three to four) parameters. It is capable of resolving convoluted peaks, and the exponential-Gaussian hybrid improves the description of asymmetric peaks (i.e. fronting and tailing). The optimal data preprocessing suggested in this article consists of estimation of Gaussian peak parameters and subsequent calculation of diagnostic ratios from peak heights. We tested the method on chromatographic data from 20 replicate oil samples and found it to be less time-consuming and subjective than commercial software, and with comparable data quality.

Gas Chromatography-Mass Spectrometry↗

PubMed2005

Chemical fingerprinting of petroleum biomarkers using time warping and PCA.

A new method for chemical fingerprinting of petroleum biomakers is described. The method consists of GC-MS analysis, preprocessing of GC-MS chromatograms, and principal component analysis (PCA) of selected regions. The preprocessing consists of baseline removal by derivatization, normalization, and alignment using correlation optimized warping. The method was applied to chromatograms of m/z 217 (tricyclic and tetracyclic steranes) of oil spill samples and source oils. Oil spill samples collected from the coastal environment in the weeks after the Baltic Carrier oil spill were clustered in principal components 1 to 4 with oil samples from the tank of the Baltic Carrier (source oil). The discriminative power of PCA was enhanced by deselecting the most uncertain variables or scaling them according to their uncertainty, using a weighted least squares criterion. The four principal components were interpreted as follows: boiling point range (PC1), clay content (PC2), carbon number distribution of sterols in the source rock (PC3), and thermal maturity of the oil (PC4). In summary, the method allows for analyses of chromatograms using a fast and objective procedure and with more comprehensive data usage compared to other fingerprinting methods.

Accidents↗

PubMed2004

Halogenated organic contaminants in marine fish and mussels from southern Greenland--pilot study on relations to trophic levels and local sources.

Mussels and marine fish (shorthorn sculpin and Greenland cod) were sampled at three locations with varying human activity. Fish livers and mussels were analysed for polychlorinated biphenyls (PCBs), polybrominated diphenylethers (PBDEs) and chlorinated pesticides including chlordane and toxaphene. Levels of chlorinated contaminants in shorthorn sculpins from the background location, [capital Sigma]PCB (217-224 ng g(-1) lw), [capital Sigma]DDT (180 ng g(-1) lw) and hexachlorobenzene (32-44 ng g(-1) lw), were in the same range as previously observed in eastern Greenland but exceeded the levels previously observed in southern and western Greenland. Multivariate analysis showed that pollutant concentrations were mainly explained by trophic levels of the species (cod > sculpins > mussels). A pooled sample of shorthorn sculpins from the harbour of Qaqortoq had significantly higher PCB and PBDE concentrations with a different congener pattern compared to the background site, while other contaminants were comparable. This points towards local pollution sources, possibly accumulated emissions from burning of waste.

Animals↗

PubMed2004

Polybrominated diphenyl ethers and organochlorine compounds in biota from the marine environment of East Greenland.

Ten black guillemot eggs, 19 ringed seals, 20 shorthorn sculpins and 20 Arctic chars were collected around Ittoqqortoormiit (Scoresbysund, Central East Greenland) in summer 2001 and analysed for 11 brominated diphenyl ether congeners (BDEs) and organochlorine compounds. Congeners BDE85 and BDE183 were not detected in any sample. SigmaBDE was highest in black guillemot eggs, with a median value of 80 ng/g lipid weight. This was approximately three times higher than that found for black guillemot eggs from West Greenland, thus supporting the spatial trend observed for organochlorines in Greenland. The median SigmaBDE concentration in ringed seal blubber was 36 ng/g lipid weight. This was clearly higher than SigmaBDE concentrations in ringed seal from the Canadian Arctic, but slightly lower than those found in ringed seals from Svalbard collected in 1981 and approximately 10 times lower than levels in seals from the Baltic Sea. Adult ringed seals had significantly higher SigmaBDE concentrations than animals less than 5 years old. Shorthorn sculpin liver and Arctic char muscle had similar concentrations of SigmaBDE, both with a median value of 7-10 ng/g lipid weight. The levels in shorthorn sculpin were similar to those reported from a previous study in Southwest Greenland. SigmaBDE levels correlated with PCB, DDT and chlordane-concentrations in the same samples, indicating similar mechanisms of uptake, bioaccumulation and biomagnification. The summed chlorobiphenyl concentrations in the same samples exceeded the SigmaBDE concentrations by a factor of approximately 15-30. The BDE congener patterns in black guillemot eggs and ringed seals were investigated using compound ratios and multivariate data analysis. The intraspecies variance was relatively small for black guillemot eggs and larger for ringed seals. Ringed seals had higher relative levels of the lower BDE congeners, e.g. BDE28 and BDE47 than black guillemots. The reasons for these different accumulation patterns are largely unknown and may reflect species-related differences in pollutant exposure, bioavailablity and metabolism.

Adipose Tissue↗

PubMed2004

Integrated methodology for forensic oil spill identification.

A new integrated methodology for forensic oil spill identification is presented. It consists of GC-MS analysis, chromatographic data processing, variable-outlier detection, multivariate data analysis, estimation of uncertainties, and statistical evaluation. The methodology was tested on four groups of diagnostic ratios composed of petroleum biomarkers and ratios within homologous PAH categories. Principal component analysis (PCA) was employed and enabled the simultaneous analysis of many diagnostic ratios. Weathering was taken into account by considering the sampling uncertainties estimated from replicate spill samples. Statistical evaluation ensured an objective matching of oil spill samples with suspected source oils as well as classification into positive match, probable match, and nonmatch. The data analysis is further refined if two or more source oils are classified as probable match by using weighted least squares fitting of the principal components, local PCA models, and additional information relevant to the spill case. The methodology correctly identified the source of two spill samples (i.e., crude oils from Oseberg East and Oseberg Field Centre) and distinguished them from closely related source oils.

Denmark↗

PubMed2004

Persistent halogenated compounds in black guillemots (Cepphus grylle) from Greenland--levels, compound patterns and spatial trends.

Twenty-seven black guillemot eggs and 39 livers were analysed for polychlorinated biphenyls (PCBs), chlorinated pesticides including chlordane-related compounds and toxaphene, and polybrominated diphenylethers (PBDEs). The samples were collected at Qeqertarsuaq (Godhavn, West Greenland) and Ittoqqortoormiit (Scoresbysund, East Greenland). The concentrations of halogenated organic compounds in samples from East Greenland were somewhat higher than the corresponding concentrations from West Greenland. Differences in compound patterns were found between West and East Greenland, with higher percentages of the heavier PCB molecules, p,p(')-DDE and alpha-HCH in the samples from Ittoqqortoormiit. Similarly, different levels and different compositions were observed for eggs and livers. The eggs had generally higher concentrations of all compounds as well as higher percentages of CHB-50, CHB-62 and alpha-HCH than liver samples from the same area. Dividing the liver samples into age groups revealed increasing concentrations with age.

Animals↗

PubMed2002

Polybrominated diphenyl ethers (PBDEs) in marine fish and blue mussels from southern Greenland.

Levels of polybrominated diphenyl ethers (PBDEs) have not previously been reported in Greenland. In this study shorthorn sculpins (Myoxocephalus scorpius) were sampled at three locations in southern Greenland; Usuk (no population), Igaliko (population 40) and Qaqortoq (population 3200). Furthermore uvak (Gadus ogac), spotted wolffish (Anarhichas minor), starry ray (Raja radiata), and blue mussels (Mytilus edulis) were collected at Usuk. Pooled samples of fish liver and blue mussel were analysed for lower brominated PBDEs (BDE-47, BDE-99, BDE-100 and BDE-153). The highest PBDE levels were found in Qaqortoq followed by Igaliko and Usuk. The measured sum PBDE concentrations in shorthorn sculpin collected at Qaqortoq, Igaliko and Usuk, were 8.2, 3.1 and 2.1 all in units of microg kg(-1) wet weight. In female and male uvak collected at Usuk PBDE levels of 7.1 and 12.0 microg kg(-1) wet weight were measured, while the concentrations were 1.2 microg kg(-1) in spotted wolffish, 1.4 microg kg(-1) in starry ray and 0.11 microg kg(-1) in blue mussels from the same locality all measured on a wet weight basis. The highest concentrations were measured in uvak, a top-predator on fish indicating that PBDEs are biomagnifying. The level of tetra-hexa BDEs is 15-24 times lower than PCB levels measured in the same samples, except for shorthorn sculpin collected at Qaqortoq, where the level of PBDEs was 40 times lower than the level of PCBs. The high concentration of PCBs relative to PBDEs in shorthorn sculpin collected at Qaqortoq signifies a local emission of PCBs, which is higher than the local emission of PBDEs.

Animals↗