Profiling of individual naphthenic acids at a composite tailings reclamation fen by comprehensive two-dimensional gas chromatography-mass spectrometry.

Naphthenic acids (NAs) are naturally occurring in the Athabasca oil sands region (AOSR) and accumulate in tailings as a result of water-based extraction processes. NAs exist as a complex mixture, so the development of an analytical technique to characterize them has been an on-going challenge. The aim of this study was to use comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry to monitor individual NAs within a wetland reclamation site in the AOSR.

Improved coverage of naphthenic acid fraction compounds by comprehensive two-dimensional gas chromatography coupled with high resolution mass spectrometry.

This study reports the first application of comprehensive two-dimensional gas chromatography coupled to a high-resolution quadrupole time-of-flight mass spectrometer (GC×GC/HRQTOF-MS) for the characterization of naphthenic acid fraction compounds (NAFCs) from the Alberta Oil Sands. High resolution mass spectrometry (HRMS) significantly increased the coverage of NAFCs in the mixture and allowed the differentiation of NAFCs from several chemical classes. It was demonstrated that GC×GC, in combination with the high mass accuracy and precision of the HRQTOF-MS, could distinguish chemical species with the C vs SH mass split at a much lower resolving power than required with direct infusion experiments.

Age-associated metabolic dysregulation in bone marrow-derived macrophages stimulated with lipopolysaccharide.

Macrophages are major contributors to age-associated inflammation. Metabolic processes such as oxidative phosphorylation, glycolysis and the urea cycle regulate inflammatory responses by macrophages. Metabolic profiles changes with age; therefore, we hypothesized that dysregulation of metabolic processes could contribute to macrophage hyporesponsiveness to LPS.

Evaluation of Firefighter Exposure to Wood Smoke during Training Exercises at Burn Houses.

Smoke from wood-fueled fires is one of the most common hazards encountered by firefighters worldwide. Wood smoke is complex in nature and contains numerous compounds, including methoxyphenols (MPs) and polycyclic aromatic hydrocarbons (PAHs), some of which are carcinogenic. Chronic exposure to wood smoke can lead to adverse health outcomes, including respiratory infections, impaired lung function, cardiac infarctions, and cancers.

Identification of individual thiophene-, indane-, tetralin-, cyclohexane-, and adamantane-type carboxylic acids in composite tailings pore water from Alberta oil sands.

Rationale: Naphthenic acids (NAs) accumulate in oil sands process-affected water (OSPW) as a result of the water-based extraction processes, and represent one of the toxic fractions in OSPW. They exist as a complex mixture and so the development of an analytical method to characterize and quantify individual acids has been an on-going challenge. The multidimensional separation technique of two-dimensional gas chromatography (GC × GC) has the potential to provide a fingerprint of the sources of NAs and can potentially resolve individual analytes for target analysis.

Identification of the halogenated compounds resulting from the 1997 Plastimet Inc. fire in Hamilton, Ontario, using comprehensive two-dimensional gas chromatography and (ultra)high resolution mass spectrometry.

Between July 9-12, 1997, at least 400 tonnes of polyvinyl chloride (PVC) were consumed in a fire at the Plastimet Inc. plastics recycling facility in Hamilton, Ontario, Canada. This led to the release of contaminants, including highly toxic polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF).

Comprehensive and simultaneous coverage of lipid and polar metabolites for endogenous cellular metabolomics using HILIC-TOF-MS.

The comprehensive metabolomic analyses using eukaryotic and prokaryotic cells are an effective way to identify biomarkers or biochemical pathways which can then be used to characterize disease states, differences between cell lines or inducers of cellular stress responses. One of the most commonly used extraction methods for comprehensive metabolomics is the Bligh and Dyer method (BD) which separates the metabolome into polar and nonpolar fractions. These fractions are then typically analysed separately using hydrophilic interaction liquid chromatography (HILIC) and reversed-phase (RP) liquid chromatography (LC), respectively.

Tandem LC columns for the simultaneous retention of polar and nonpolar molecules in comprehensive metabolomics analysis.

The tandem use of hydrophilic interaction LC columns with RP columns in series configuration has resulted in the retention of both polar and nonpolar components in complex biological samples (mouse serum) in a single analysis. This approach successfully coupled various columns with orthogonal separation characteristics, employed a single solvent gradient program compatible with the two columns and used ESI coupled to a TOF mass spectrometer for detection. Ion suppression, a common problem in ESI, was virtually eliminated for components eluting with apparent capacity factors >0.

Dechlorane plus monoadducts in a Lake Ontario (Canada) food web and biotransformation by lake trout (Salvelinus namaycush) liver microsomes.

Compounds related to the high-production-volume flame retardant Dechlorane Plus (DP) were measured in a Lake Ontario food web located downstream of a DP manufacturing plant. These compounds, 1,3- and 1,5-DP-monoadducts (DPMA), are positional isomers and are thought to arise from the incomplete reaction of DP or impurities in the DP starting material during its manufacture. The 1,3-DPMA isomer was measured (0.

Transcriptomic and metabolomic analysis of Yukon Thellungiella plants grown in cabinets and their natural habitat show phenotypic plasticity.

Background: Thellungiella salsuginea is an important model plant due to its natural tolerance to abiotic stresses including salt, cold, and water deficits. Microarray and metabolite profiling have shown that Thellungiella undergoes stress-responsive changes in transcript and organic solute abundance when grown under controlled environmental conditions. However, few reports assess the capacity of plants to display stress-responsive traits in natural habitats where concurrent stresses are the norm.

Dechlorane plus and related compounds in the environment: a review.

Dechlorane Plus (DP) is a high production volume, chlorinated flame retardant. Despite its long production history, it was only recently found in the environment. The first "sightings" of DP were in the North American Great Lakes, but subsequent work has indicated that DP is a global contaminant.

Identification of phosphomethylethanolamine N-methyltransferase from Arabidopsis and its role in choline and phospholipid metabolism.

Three sequential methylations of phosphoethanolamine (PEA) are required for the synthesis of phosphocholine (PCho) in plants. A cDNA encoding an N-methyltransferase that catalyzes the last two methylation steps was cloned from Arabidopsis by heterologous complementation of a Saccharomyces cerevisiae cho2, opi3 mutant. The cDNA encodes phosphomethylethanolamine N-methyltransferase (PMEAMT), a polypeptide of 475 amino acids that is organized as two tandem methyltransferase domains.

A comparative study of two factor analytic models applied to PAH data from inhalable air particulate collected in an urban-industrial environment.

Two factor analysis (FA)-based receptor modeling methods were applied to a polycyclic aromatic hydrocarbon (PAH) dataset from extracts of 75 PM(10) air particulate samples collected concurrently at 4 sampling sites proximate to the urban-industrial area in Hamilton, Ontario, Canada. The total PAH concentrations of 48 target compounds ranged from 0.23 to 172 ng m(-3).

Evaluation of PAH diagnostic ratios as source apportionment tools for air particulates collected in an urban-industrial environment.

A variety of polycyclic aromatic hydrocarbon (PAH) diagnostic ratios were examined as source apportionment tools in the analysis of a PAH data set associated with atmospheric particulate matter collected in an urban-industrial environment. Seventy-six PM(10) samples were collected concurrently at 4 sampling sites over a one-month period in Hamilton, Ontario, Canada, a city of 500 000 people that is home to two integrated steel companies, associated industries and a network of roadways and major highways. Samples collected under well defined meteorological conditions were categorized as being 'upwind' or 'downwind' of the industrial sector.

Compounds structurally related to Dechlorane Plus in sediment and biota from Lake Ontario (Canada).

The historical occurrence of Dechlorane Plus (DP) and detection of novel compounds structurally related to DP is described in a dated Lake Ontario sediment core. Our core was collected near the mouth of the Niagara River, which is known to be a major source of DP to the lake. Maximum DP concentrations (920 ng g(-1), dry weight) were observed between 1976 and 1980, the highest reported to date.

A shotgun lipidomics study of a putative lysophosphatidic acid acyl transferase (PlsC) in Sinorhizobium meliloti.

A shotgun lipidomics approach was used to study the knockout mutant of a putative lysophosphatidic acyl acid transferase (PlsC) in order to delineate the function of this enzyme in Sinorhizobium meliloti. In plsC knockout mutant lipids that contained 16:0 and 16:1 fatty acids and their biosynthetically related cyclopropane fatty acid (cis-9,10-methylene hexadecanoic acid) decreased up to 93%. Tandem mass spectrometry experiments in the presence of added Li(+) showed that the putative PlsC (SMc00714) functioned as a lysophosphatidic acid acyl transferase specific for the transfer of C16 fatty acids to the sn-2 position of lipids.

Cyclopropane fatty acyl synthase in Sinorhizobium meliloti.

Cyclopropane fatty acyl synthases (CFA synthases) are enzymes that catalyse the addition of a methylene group across cis double bonds of monounsaturated fatty acyl chains in lipids. We have investigated the function of two putative genes, cfa1 and cfa2, proposed to code for CFA synthases in Sinorhizobium meliloti. Total fatty acid composition and fatty acid distributions within lipid classes for wild-type and cfa1 and cfa2 mutant strains grown under Pi starvation and in acidic culture conditions were obtained by GC/MS and by infusion ESI/MS/MS, respectively.

A shotgun lipidomics approach in Sinorhizobium meliloti as a tool in functional genomics.

A shotgun lipidomics approach that allowed the analysis of eight lipid classes directly from crude extracts of the soil bacterium Sinorhizobium meliloti is presented. New MS-MS transitions are reported for the analysis of monomethylphosphatidylethanolamines, dimethylphosphatidylethanolamines, and three bacterial non-phosphorus-containing lipid classes [sulfoquinovosyldiacylglycerols, ornithines, and diacylglyceryl-(N,N,N-trimethyl)-homoserines]. Unique MS-MS transitions allowed the analysis of isomeric species from various lipid classes without chromatography.

Levels and isomer profiles of dechlorane plus in Chinese air.

The highly chlorinated flame retardant, Dechlorane Plus (DP), was measured in air across 97 Chinese urban and rural sites. DP was detected in 51 of these sites, with a mean air concentration in urban centers (15.6 +/- 15.

Source apportionment of PAH in Hamilton Harbour suspended sediments: comparison of two factor analysis methods.

A total of 26 suspended sediment samples collected over a 5-year period in Hamilton Harbour, Ontario, Canada and surrounding creeks were analyzed for a suite of polycyclic aromatic hydrocarbons and sulfur heterocycles. Hamilton Harbour sediments contain relatively high levels of polycyclic aromatic compounds and heavy metals due to emissions from industrial and mobile sources. Two receptor modeling methods using factor analyses were compared to determine the profiles and relative contributions of pollution sources to the harbor; these methods are principal component analyses (PCA) with multiple linear regression analysis (MLR) and positive matrix factorization (PMF).

Comparison of three GC/MS methodologies for the analysis of fatty acids in Sinorhizobium meliloti: development of a micro-scale, one-vial method.

Three protocols for fatty acid analysis in Sinorhizobium meliloti were improved by the addition of a number of standards/controls and a silylation step which allowed the determination of recoveries, extents of conversion of lipids to fatty acid methyl esters (FAMEs) and extents of side reactions. Basic hydrolysis followed by acid-catalyzed methylation and transmethylation with sodium methoxide, were the best for the analysis of 3-hydroxy- and cyclopropane fatty acids, respectively. A micro-scale, one-vial method that employed sodium methoxide/methanol was equally efficient and on a 1000-fold smaller scale than standard methods.

Dechlorane plus levels in sediment of the lower Great Lakes.

A recently discovered chlorinated flame retardant, Dechlorane Plus (DP), was reported in air and a sediment core within the North American Great Lakes region. To further reveal the fate of DP in the Great Lakes, 40 surficial sediments from Lakes Erie and Ontario and two additional cores were analyzed using newly available analytical grade DP isomer solutions. The maximum total concentration in Lake Ontario was over 60-fold higher than Lake Erie, 586 ng/g and 8.

Refined tunable methodology for characterization of contaminant-particle relationships in surface water.

To understand contaminant transport in aquatic systems, it is essential to define the physical characteristics of the primary particulate carriers. The distribution of organic pollutants with particle-size class and particle morphology in a freshwater embayment (Hamilton Harbor, western Lake Ontario) was studied using a sequence of novel sample preparation and characterization techniques. Water samples (24 L) were fractionated according to particle-size distribution using differential cascade sedimentation and centrifugation methods.