Organic geochemistry of the British Kimmeridge Clay: 1. Composition of shale oils produced from Kimmeridge sediments

A series of shale oils produced by Fischer assay of Upper Jurassic Kimmeridgian oil shales, claystones and cementstones from on-shore Britain has been analysed. Oil yields are related to lithology via the quantity of sedimentary organic matter present in each lithologic unit, and also to stratigraphic horizon for certain rich, laterally uniform and persistent units. Shale oils are dark and sulphurous, containing < 50% hydrocarbons. NSO compounds are relatively important in the chromatographically separable fractions, while aliphatic hydrocarbons are usually subordinate. Unimodal normal alkane distributions maximize around nC16, while bimodal distributions have a secondary maximum around nC29. Many alkane gas chromatograms are characterized by a prominent peak due to the nC23 alkane. Certain compositional features are of pyrolytic origin (aromatics, heterocompounds, alkenes), while others are determined by the organic sedimentary input (alkane distributions, prominent nC23 alkane). Broad similarity in geochemical parameters suggests a consistency in the composition of sedimented organic matter. Smaller-scale compositional variations are thought to result from minor fluctuations in the composition of the organic sedimentary input, for example changes in the amount of terrestrial organic detritus reaching the depocentre. Results suggest a dominantly algal or bacterial organic matter source continuously operative throughout much of the Upper Jurassic over the entire region, with a smaller, more variable magnitude contribution from terrestrial sources, probably deposited in a near-shore marine shelf-sea environment under anoxic conditions.     

Residues of organochlorine pesticides in vegetables marketed in Greater Accra Region of Ghana

Residual levels of organochlorine pesticides (OCPs) were determined in 240 samples of vegetables collected from selected markets from Greater Accra region of Ghana in July 2010 to February 2011. The determination was done using gas chromatography with electron capture detector (GC-ECD). The compounds targeted were lindane, heptachlor + its epoxide, endrin, dieldrin, o,p′-DDE, p,p′-DDE, o,p′-DDD, o,p′-DDT and p,p′-DDT. The results indicated that all the vegetables sampled had some levels of one or more OCPs in them. Residues of pesticides were found in 71.9% of all the vegetable samples analyzed indicating high incidence of these xenobiotics in the vegetables from the markets and 31.48% samples were above the maximum residue levels (MRLs). The most frequently found and abundant pesticides were the metabolites of DDT (o,p′-DDE, p,p′-DDE and o,p′-DDD), followed by lindane and then o,p′-DDT. The residue levels and the detection rate of the OCPs indicate that, vegetables from supermarket had higher OCPs levels, followed by roadside grocery stores and open markets. The results recommend the need for regular monitoring of a greater number of samples for long periods for pesticide residues especially in fruits and vegetables to protect consumers’ health.     

Identification of the carboxylic acid functionality by using electrospray ionization and ion-molecule reactions in a modified linear quadrupole ion trap mass spectrometer

A mass spectrometric method has been developed for the identification of the carboxylic acid functional group in analytes evaporated and ionized by electrospray ionization (ESI). This method is based on gas-phase ion-molecule reactions of ammoniated ([M + NH4]+) and sodiated ([M + Na]+) analyte molecules with trimethyl borate (TMB) in a modified linear quadrupole ion trap mass spectrometer. The diagnostic reaction involves addition of the deprotonated analyte to TMB followed by the elimination of methanol. A variety of analytes with different func-tionalities were examined, and this reaction was only observed for molecules containing the carboxylic acid functionality. The selectivity of the reaction is attributed to the acidic hydrogen present in the carboxylic acid group, which provides the proton necessary for the elimination of methanol. The diagnostic products are easily identified based on the m/z value of the product ion, which is 72 Th (thomson) greater than the m/z value of the charged analyte, and also by the character-istic isotope pattern of boron. The applicability of this method for pharmaceutical analysis was demonstrated for three nonsteroidal anti-inflammatory drugs: ibuprofen, naproxen, and ketoprofen.     

Organic geochemistry of the British Kimmeridge clay: 2. Acyclic isoprenoid alkanes in Kimmeridge shale oils

The C15---C20 isoprenoid alkane composition of Kimmeridge Clay shale oils produced by Fischer assay has been examined, and compared with the isoprenoid composition of corresponding bitumens. C16 and C18 isoprenoid alkanes are generally dominant in shale oils, while pristane (C19) and phytane (C20) dominate in bitumens. A significant proportion of the phytane in many shale oils is derived from simple evaporation of free (bitumen) phytane, while free pristane contributes less to shale oil composition. Some shale oil phytane and a large proportion of pristane is kerogen-derived. Certain shale oils contain lower concentrations of isoprenoid alkanes than corresponding bitumens, suggesting that some free alkane is thermally degraded during pyrolysis. Results thus indicate three sources for shale oil isoprenoid alkanes: thermal evaporation of free alkanes (particularly for phytane), kerogen decomposition, and possibly the cracking of higher homologues for C15---C19 alkanes. Kerogen-derived isoprenoids are suggested to arise by thermal desorption of adsorbed free alkane (particularly for phytane) and from C---O and C---C bonded species (excluding phytane) via postulated clay catalysed hydrogenation of initially formed alkenes. Comparison of shale oil and bitumen pristane/phytane ratios allows groups of oil shales to be defined, dependent on source composition, organic carbon content and maturity. Shale oil pristane/phytane ratios can also help to determine depositional environments and source composition, although maturity, shale mineralogy and competing alkene-forming pyrolytic reactions may also affect the ratios.     

The Mitochondrial Epigenome: An Unexplored Avenue to Explain Unexplained Myopathies?

Mutations in either mitochondrial DNA (mtDNA) or nuclear genes that encode mitochondrial proteins may lead to dysfunctional mitochondria, giving rise to mitochondrial diseases. Some mitochondrial myopathies, however, present without a known underlying cause. Interestingly, methylation of mtDNA has been associated with various clinical pathologies. The present study set out to assess whether mtDNA methylation could explain impaired mitochondrial function in patients diagnosed with myopathy without known underlying genetic mutations. Enhanced mtDNA methylation was indicated by pyrosequencing for muscle biopsies of 14 myopathy patients compared to four healthy controls, at selected cytosines in the Cytochrome B (CYTB) gene, but not within the displacement loop (D-loop) region. The mtDNA methylation patterns of the four healthy muscle biopsies were highly consistent and showed intriguing tissue-specific differences at particular cytosines with control skin fibroblasts cultured in vitro. Within individual myopathy patients, the overall mtDNA methylation pattern correlated well between muscle and skin fibroblasts. Despite this correlation, a pilot analysis of four myopathy and five healthy fibroblast samples did not reveal a disease-associated difference in mtDNA methylation. We did, however, detect increased expression of solute carrier family 25A26 (SLC25A26), encoding the importer of S-adenosylmethionine, together with enhanced mtDNA copy numbers in myopathy fibroblasts compared to healthy controls. To confirm that pyrosequencing indeed reflected DNA methylation and not bisulfite accessibility, mass spectrometry was employed. Although no myopathy-related differences in total amount of methylated cytosines were detected at this stage, a significant contribution of contaminating nuclear DNA (nDNA) was revealed, and steps to improve enrichment for mtDNA are reported. In conclusion, in this explorative study we show that analyzing the mitochondrial genome beyond its sequence opens novel avenues to identify potential molecular biomarkers assisting in the diagnosis of unexplained myopathies.