Total Organic Extract Research Articles

Toxicological and Mutagenic Effects of Particulate Matter from Domestic Activities.

People spend most of their time indoors, particularly in their houses where daily activities are carried out, enhancing particulate matter (PM) emissions with consequent adverse health impacts. This study intended to appraise the toxicological and mutagenic responses of particulate matter with a diameter less than 10 μm (PM10) released from cooking and ironing activities under different conditions. The cytotoxicity of the PM10 total organic extracts was tested in A549 cells using the WST-8 and the lactate dehydrogenase (LDH) assays, while the interference in cell cycle dynamics and reactive oxygen species (ROS) production was analysed by flow cytometry. The S. typhimurium TA98 and TA100 Ames tester strains with and without metabolic activation were employed to determine the mutagenic potential of the PM10-bound polycyclic aromatic hydrocarbons (PAHs). PM10 organic extracts decreased the metabolic activity of A549 cells; however, no effects in the LDH release were observed. An increase in ROS levels was registered only for cells treated with PM10 at IC20 from steam ironing, in low ventilation conditions, while cell cycle dynamics was only affected by exposure to PM10 at IC20 from frying horse mackerel and grilling boneless pork strips. No mutagenic effects were observed for all the PM10-bound PAHs samples.

Anti-inflammatory, antioxidant, cytotoxic activities, and sesquiterpenoid contents of Paralemnalia thyrsoides

Background and Objectives: Paralemnalia thyrsoides is an octocoral species of the family Nephtheidae. It has established as platform for the production of a varied array of sesquiterpenoids such as africanane, nardosinane, and neolemnane -type compounds. Antiviral and cytotoxic effects of sesquiterpenes from P. thyrsoides were reported. Materials and Methods: The animal sample of P. thyrsoides was repeatedly extracted with organic solvents. Then, the animal extract was fractionated and purified employing different planar chromatographic methods. The chemical structures of all isolated metabolites were identified by employing spectroscopic tools (ultraviolet [UV], IR, and nuclear magnetic resonance) along with MS. The anti-inflammatory activity (membrane stabilization%), and histamine release inhibitory effect, the antioxidant activity using 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay, along with cytotoxic activity against four-cancer cells: hepatocellular carcinoma (Hep G-2), colon (HCT-116), prostate (PC-3), and breast (MCF-7) cancers were evaluated. Results: Three new sesquiterpenoids along with two known ones and a gorgostane steroid. The three new sesquiterpenoids were identified as eudesma-1, 2, 15-trihydroxy-3-en-7-one (1), eudesma-1, 2, 15-trihydroxy-5-ene (2), and nardosinanol J (3). Whereas the known compounds were identified as lemnolin A (4) and gorgostane (5). The in-vitro assays results revealed that the total organic extract showed anti-inflammatory activity (membrane stabilization %) with IC50 of 88.3 ± 1.2 compared to positive control (indomethacin with IC50 of 17.02 ± 1.2 μg/ml) and strong histamine release inhibitory effect with IC50 of 17.94 ± 1.08 compared to a positive control (diclofenac with IC50 of 17.94 ± 1.26 μg/ml). It also showed that the total organic extract has antioxidant activity using DPPH assay with an IC50 of 157.5 ± 4.24μg/ml. Moreover, the total organic extract has strong inhibitory activities against Hep G-2 with an IC50 of 12.1 ± 1.1 μg/ml, HCT-116 with an IC50 of 13.4 ± 1.8 μg/ml, PC-3 with an IC50 of 28.6 ± 2.7 μg/ml, and good inhibitory activity against MCF-7 with an IC50 of 49.0 ± 3.9 μg/ml. Conclusion: The observed bioactivity and the variety of carbon skeletons isolated warrants further work on the constituents of P. thyrsoides.

Microalgae and Cyanobacteria Strains as Producers of Lipids with Antibacterial and Antibiofilm Activity.

Lipids are one of the primary metabolites of microalgae and cyanobacteria, which enrich their utility in the pharmaceutical, feed, cosmetic, and chemistry sectors. This work describes the isolation, structural elucidation, and the antibiotic and antibiofilm activities of diverse lipids produced by different microalgae and cyanobacteria strains from two European collections (ACOI and LEGE-CC). Three microalgae strains and one cyanobacteria strain were selected for their antibacterial and/or antibiofilm activity after the screening of about 600 strains carried out under the NoMorFilm European project. The total organic extracts were firstly fractionated using solid phase extraction methods, and the minimum inhibitory concentration and minimal biofilm inhibitory concentration against an array of human pathogens were determined. The isolation was carried out by bioassay-guided HPLC-DAD purification, and the structure of the isolated molecules responsible for the observed activities was determined by HPLC-HRESIMS and NMR methods. Sulfoquinovosyldiacylglycerol, monogalactosylmonoacylglycerol, sulfoquinovosylmonoacylglycerol, α-linolenic acid, hexadeca-4,7,10,13-tetraenoic acid (HDTA), palmitoleic acid, and lysophosphatidylcholine were found among the different active sub-fractions selected. In conclusion, cyanobacteria and microalgae produce a great variety of lipids with antibiotic and antibiofilm activity against the most important pathogens causing severe infections in humans. The use of these lipids in clinical treatments alone or in combination with antibiotics may provide an alternative to the current treatments.

Establishing a link between composition and toxicity of offshore produced waters using comprehensive analysis techniques – A way forward for discharge monitoring?

Extracts of produced waters from five mature Norwegian Sea oil fields were examined as total organic extracts (TOEs) and after fractionation into operationally-defined ‘polar’ and ‘apolar’ fractions. The TOEs and fractions were examined by gas chromatography (GC), GC-mass spectrometry (GC–MS), two dimensional GC–MS (GC × GC–MS) and liquid chromatography with high-resolution spectrometry (LC-HRMS) techniques.Low molecular weight aromatics, phenols and other common petroleum-derived hydrocarbons were characterized and quantified in the TOEs and fractions. In addition, a range of more uncommon polar and apolar constituents, including those likely derived from production chemicals, such as trithiolane, imidazolines and quaternary amine compounds (so-called ‘quats’), were tentatively identified, using GC × GC–MS and LC-HRMS.The acute toxicity of the TOEs and subfractions was investigated using early life stages of the marine copepod Acartia tonsa. Toxicity varied significantly for different PW TOEs and subfractions. For some PWs, the toxicity was attributed mainly to the ‘polar’ components, while that of other PWs was associated mainly with the ‘apolar’ components. Importantly, the observed toxicity could not be explained by the presence of the commonly reported compounds only.Although, due to the vast chemical complexity even of the sub-fractions of the PW extracts, specific compounds driving the observed toxicity could be not be elucidated in this study, the proposed approach may suggest a way forward for future revisions of monitoring regimes for PW discharges.

The molecular composition of Cretaceous ambers: Identification and chemosystematic relevance of 1,6-dimethyl-5-alkyltetralins and related bisnorlabdane biomarkers

One of the major components of the organic solvent extractable fraction of Cretaceous ambers is 1,6-dimethyl-5-isopentyltetralin, a compound that has been incorrectly or not identified in previous reports on the molecular composition of Cretaceous ambers. Here, the purification and structural identification of 1,6-dimethyl-5-isopentyltetralin is reported from amber samples of the Cretaceous Peñacerrada II deposit at Peñacerrada, Álava (Basque-Cantabrian Basin, Spain). The structural identification of 1,6-dimethyl-5-isopentyltetralin allowed the complete identification of related compounds, comprising the family of 1,6-dimethyl-5-alkyltetralins. This suggests that those compounds, with concentrations up to 27% of the total organic extract of amber from Peñacerrada, are characteristic for labdane-type biomarkers in Cretaceous fossil resins and their distributions indicate different compositional families, related to their botanical and topographic origin. Also, the name amberene is proposed for the main molecule of this group. The relative proportion of the amberene-type compounds suggests three compositional families for the Cretaceous Spanish ambers.

High levels of acrylate in the Great Barrier Reef coral Acropora millepora

High concentrations of acrylate, 542–683 μmol g−1 of the non-skeletal dry mass (DM), were measured in the Great Barrier Reef coral, Acropora millepora, using quantitative nuclear magnetic resonance spectroscopy (qNMR). As the amount of NaCl salt in the samples was substantial but variable, the total carbon (TC) in the coral extracts was determined, and the carbon due to acrylate found to represent 13–15% of the TC present in the total organic extracts (TOE). Acrylate, a C3 compound, is thus a substantial carbon source in the coral holobiont and is known to be derived from dimethylsulfoniopropionate (DMSP), which has previously been found in corals and other organisms that harbor Symbiodinium spp. The reason for such high levels of acrylate in the corals is unknown; possible functions include antimicrobial and/or antioxidant roles, as well as playing a role in the structuring of the healthy resident coral bacteria.

A preliminary characterization of the mutagenicity of atmospheric particulate matter collected during sugar cane harvesting using the Salmonella/microsome microsuspension assay

During sugar cane harvesting season, which occurs from May to November of each year, the crops are burnt, cut, and transported to the mills. There are reports showing that mutagenic activity and PAH content increase during harvesting season in some areas of São Paulo State in comparison with nonharvesting periods. The objective of this work was to preliminarily characterize the mutagenic activity of the total organic extracts as well as corresponding organic fractions of airborne particulate matter (PM) collected twice from two cities, Araraquara (ARQ) and Piracicaba (PRB), during sugar cane harvesting season using the Salmonella/microsome microssuspension assay. One sample collected in São Paulo metropolitan area was also included. The mutagenicity of the total extracts ranged from 55 to 320 revertants per cubic meter without the addition of S9 and from not detected to 57 revertants per cubic meter in the presence of S9 in areas with sugar cane plantations. Of the three fractions analyzed, the most polar ones (nitro and oxy) were the most potent. A comparison of the response of TA98 with YG1041 and the increased potencies without S9 indicated that nitro compounds are causing the observed effect. More studies are necessary to verify the sources of the mutagenic activity such as burning of vegetal biomass and combustion of heavy duty vehicles used to transport the sugar cane to the mills. The Salmonella/microsome assay can be an important tool to monitor the atmosphere for mutagenicity during sugar cane harvesting season.

A direct and simple method of coupling matrix-assisted laser desorption and ionization time-of-flight mass spectrometry (MALDI-TOF MS) to thin-layer chromatography (TLC) for the analysis of phospholipids from egg yolk

Although the most important application of matrix-assisted laser desorption and ionization time-of-flight mass spectrometry (MALDI-TOF MS) is "proteomics," there is growing evidence that this soft ionization method is also useful for phospholipid (PL) analysis. Although all PLs are detectable by MALDI-TOF MS, some lipid classes, particularly those with quaternary amines such as phosphatidylcholines (PCs), are more sensitively detected than others, and these suppress the signals of less sensitively detected PLs when complex mixtures are analyzed. Therefore, a separation of the total organic extract into individual lipid classes is necessary. As MALDI uses a solid sample, the direct evaluation of thin-layer chromatography (TLC) plates is possible. We report here on a method of directly coupling MALDI-TOF MS and TLC that can be easily implemented on commercially available MALDI-TOF devices. A total extract of hen egg yolk is used as a simple PL mixture to demonstrate the capabilities of this method. It will be shown that "clean" spectra without any major contributions from fragmentation products and matrix peaks can be obtained, and that this approach is even sensitive enough to detect the presence of PLs at levels of less than 1% of the total extract.

Analysis of archaeal core ether lipids using Time of Flight-Secondary Ion Mass Spectrometry (ToF-SIMS): Exploring a new prospect for the study of biomarkers in geobiology.

The capability of Time of Flight-Secondary Ion Mass Spectrometry (ToF-SIMS) of analysing molecular archaeal biomarkers in geobiological samples was tested and demonstrated. Using a bismuth cluster primary ion source, isopranyl glycerol di- and tetraether core lipids were detected in small amounts of total organic extracts from methanotrophic microbial mats, simultaneously and without further chemical treatment and chromatographic separation. ToF-SIMS was also employed to track the distribution of fossilized ether lipids in a massive carbonate (aragonite) microbialite that precipitated as a result of the microbial anaerobic oxidation of methane. An unambiguous signal was obtained when analysing a freshly broken rock surface (base of a microdrill core). Though some limitation occurred due to µm-topographical effects (sample roughness), it was possible to display the abundance of high molecular weight (C86 ) of tetraethers exposed in particular regions of the rock surface. 'Molecular mapping' revealed that a part of these molecules was encased within the rock fabric in a cluster-like distribution that might trace the arrangement of the calcifying microbial colonies in the once active mat system. The results reveal promising perspectives of ToF-SIMS for (i) the quasi-nondestructive analysis of lipids in extremely small geobiological samples at low concentrations; (ii) resolving the spatial distribution of these compounds on a µm2 - to cm2 -scale; and (iii) the more exact assignment of lipid biomarkers to their biological source.

Composition of extractable organic matter of air particles from rural and urban Portuguese areas

Atmospheric particulate matter (PM 10) was collected simultaneously at three sites in the West Coast of Portugal, during an intensive campaign in August 1996. The sites were located in line with the breezes blowing from the sea. The collected aerosol was analysed in relation to black and organic carbon content. The particulate organic matter was extracted with solvents and characterised by gas chromatography and mass spectrometry (GC–MS). Most of the organic mass identified consists of alkanes, polycyclic aromatic hydrocarbons (PAH), ketones, aldehydes, alcohols and fatty acids with both biogenic and anthropogenic origin. Many photochemical products from volatile organic compounds emitted by vegetation were also detected. Biomarkers such as 6,10,14-trimethylpentadecanone, abieta-8,11,13-trien-7-one and Patchouli alcohol were observed at higher concentrations in the rural sites. Samples from the urban site present lower values of “carbon preference index” and higher concentrations of petrogenic/pyrogenic species, such as PAH. The PM 10 concentrations and the total organic extract measured for the more interior site were generally lower, indicating that dispersion and dry deposition into the forest canopy were more important during the transport of the air masses than aerosol production by condensation and photochemical reactions. On the contrary, the ratio between organic and black carbon was, in general, lower at sites near the coast, especially for compounds that evaporate at lower temperatures. The organic aerosol composition also seems to be strongly dependent on the meteorology.

Ethyl Anthranilate, Ethyl Cinnamate, 2,3-Dihydrocinnamate, and Methyl Anthranilate: Four Important Odorants Identified in Pinot noir Wines of Burgundy

Ethyl anthranilate (ethyl 2-aminobenzoate), ethyl cinnamate (ethyl 3-phenyl-2-propenoate), ethyl 2,3-dihydrocinnamate (ethyl 3-phenylpropanoate), and methyl anthranilate (methyl 2-aminobenzoate) were identified, by coupled gas chromatographic-mass spectrometric analysis, as minor constituents in Burgundy Pinot noir wines. The four potent odorants were identified in a volatile fraction obtained by adsorption chromatography on silica gel of the total organic extract of wine. The results of gas-chromatography/ olfactometry analysis revealed that ethyl anthranilate was the most intense flavor compound of the isolated fraction among the four odorants identified. The second most intense flavor compound was ethyl cinnamate, followed by ethyl 2,3-dihydrocinnamate, and finally by methyl anthranilate. Ethyl anthranilate and ethyl 2,3-dihydrocinnamate were identified for the first time in any wine, and methyl anthranilate, was identified for the first time in a wine produced from a <i>Vitis vinifera</i> cultivar. The high olfactometric index found for ethyl cinnamate in the case of Pinot noir wine confirms the importance of this odorant in the wine flavor. The four odorant esters identified can influence the characteristic flavor quality exhibited by Pinot noir wines of Burgundy.

Structure determination by deuterium labelling of a sulfur-bound petroporphyrin

Structural characterization (MS, NMR) of the major porphyrin 4(D) released by desulfurization of the total organic extract of Gibellina marl (Upper Miocene, Sicily) with deuterated nickel boride disclosed the main position of attachment of this porphyrin to the macromolecular network. Chlorophyll metabolites from diatoms bearing a 7 + 5 membered ring system are likely biological precursors which could be selectively incorporated via a C-17‴ ketone and preserved in the macromolecular fractions of this S-rich sediment.

Ambient air pollutants in upper Silesia: partial chemical composition and biological activity.

The air monitoring system in Upper Silesia has provided abundant data on airborne pollutants. Air quality in this region is bad: a concentration of several gases, volatile compounds, metals, and complex mixtures of organic compounds carried by small particulate matter exceeds both daily and yearly admissible levels. About 250 individual polycyclic aromatic hydrocarbonds (PAHs) were identified in airborne pollutants, and hundreds of not identified compounds are seen on gas chromatographic profiles as minor peaks. Among PAHs are present compounds with known carcinogenic potency for humans. Seasonal variation with distinctly lower concentration of pollutants in summer than in winter was noticed. Fifteen PAHs including benzo[a]pyrene (B[a]P) determined by GC-MS method in 20 measuring points showed constant relative proportions. Thus B[a]P could be used as a representative compound for other PAHs. In urban areas, a core of Silesia values for B[a]P concentration ranged from 60 to 90 ng/m3 in winter to 5 to 20 micrograms/m in summer. Mutagenicity tested on Salmonella strains showed seasonal variation with distinctly higher values in winter. Environmentally exposed humans showed a higher level of PAH-DNA adducts in WBC than the control population from rural area. Total organic extract of small particulate matter exhibited both direct and indirect mutagenic activity, induced formation of micronuclei in bone marrow cells of BALB/c mice, induced chromosomal rearrangements, and increased sister chromatid exchange index.

Extraction of bound porphyrins from sulphur-rich sediments and their use for reconstruction of palaeoenvironments

PORPHYRINS, which are present in most sediments and crude oils, represent the 'molecular fossils' of compounds such as chlorophylls, bacteriochlorophylls and haems in the organisms from which the organic material is derived1–4. They have the potential to provide information about palaeoenvironmental conditions at the time of deposition5–9. Porphyrins derived from degradation of chlorophylls are of particular interest because of the possibility of relating palaeoproductivity estimates from sediments to chlorophyll-based measurements of present-day productivity determined by remote sensing. But standard analytical methods do not detect all of the porphyrins present in a geological sample — a substantial fraction of the porphyrins may be bound to kerogen10,11 or to solvent-extractable macromolecules, or may be degraded by the oxidative extraction procedures. It has been shown recently12–16 that sulphur may play a crucial part in binding 'biomarker' molecules at an early stage of sediment diagenesis, and that desulphurization using Raney nickel may liberate small molecules bound to sulphur-containing species. Here we show that this approach releases large amounts of porphyrins from the total organic extract of a sulphur-rich marl. Liberating bound porphyrins in this way may greatly enhance the amount of information on palaeoenvironments that can be extracted from geochemical analysis of sediments.

Les polluants organiques dans les effluents urbains et apports polluants dans millieu marin. cas du littoral Francais

Urban sewage represents an obvious source of pollution of the aquatic environment. Thus Gossett et al. (1983) identified 101 organic substances in Los Angeles urban wastes, 36 of them are on the list of priority pollutants drawn up by the EPA. Similar studies were attempted to analyze organic pollutants in different municipal sewage collected from French towns located along marine shoreline (Toulon, Marseille) or estuaries (Nantes, Morlaix). Several groups of organic pollutants were measured: hydrocarbons, high-molecular-weight halogenated hydrocarbons, volatile halogenated hydrocarbons, chlorophenols and anionic detergents. Concentrations were measured both in raw sewage and in effluents after passing through treatment plants. Average daily emission rates per capita were estimated. They vary greatly, depending on the parameters measured, suspended matter: 44–71 g; total organic extract: 11–20 g; anionic detergents: 2.2–6.6 g; total hydrocarbons: 0.2–1.8 g; aromatic hydrocarbons: 4–17 mg; chlorinated solvents: 0.1–6.0 mg; pentachlorophenol: 40–110 μg; PCBs: 10–60 μg; chlorinated insecticides (ΣDDT, lindane): ⩽ 2–60 μg. The quantities of organic pollutants actually discharged into the aquatic environment depend on whether or not purification treatment is carried out and on the nature of that treatment. Three major processes for eliminating organic pollutants are used during treatment: elimination by adsorption on suspended matter at the primary sedimentation stage and on activated sludge; elimination by gas stripping during prolonged aeration in secondary biological treatment; elimination by bacterial degradation during secondary biological treatment. Assessment of elimination of identified compounds was attempted, according to the chemical nature of organic pollutants and sewage treatment systems. Primary treatment system enables an elimination of about 50% of most organic pollutants, which is similar to the removal percentage of suspended matter. In secondary biological treatment plants, elimination rates of the majority of organic pollutants are more important, greater than 90%. Notable exceptions were also observed, especially for lindane and pentachlorophenol. These two exceptions have already been reported by the work carried out in pilot experiments by Petrasek et al. (1983). Estimations of quantities of pollutants actually discharged annually into estuarine or coastal marine waters are given. The quantities vary greatly depending on the importance of the volume of sewage, the sewage treatment system and the nature of organic pollutants. An example is given for two towns, Toulon (61,000 eq. inhab.) and Morlaix (30,000 eq. inhab.), anionic detergents: 11–72 tons; total hydrocarbons: 0.9–8.0 tons; chlorinated solvents: 0.4–40 kg; chlorinated insecticides: 0.02–1.0 kg; PCBs: 0.1–0.4 kg.

Organic indicators of groundwater pollution by a sanitary landfill

The organic composition of leachate from the Barcelona sanitary landfill is described. According to the low degree of stabilization of the disposed garbage the acid fraction accounts for 80–90% of the total organic extract. More than 50 individual organic components have been identified, indicating catabolic degradation of lipids (e.g. C 4–C 11 carboxylic acids), proteins (e.g. indole derivatives) and lignins (e.g. p-hydroxyphenyl derivatives) or simply compounds originally present in the refuse that have been washed out by percolating waters (nicotine, caffeine, phthalates). To obtain a monitoring system for the groundwater pollution originated by this landfill leachate, an analytical method is proposed based on the GC-ECD fingerprinting of groundwater acidic extracts after derivatization with PFB bromide. The chromatogram contains carboxylic and phenolic components and the profiles exhibited by waters from several test wells in the downstream edge of the landfill were indicative of the suspected leachate pollution.

Organic Geochemistry of Recent Marine Ooids as a Key to Origin of Petroleum in Oolite Reservoirs: ABSTRACT

Organic geochemical investigation of recent marine ooids (457 ± 76 to 1,516 ± 86 years) from the Schooner Cays area, Bahamas, has yielded data that suggest a probable source bed function for their ancient equivalents. Chromatographic analysis of gas desorbed from the ooids reveals the presence of C1 to C5+ compounds believed to be authigenic. These include between 1.7 and 3.6 × 10-5 gm C1 to C4 saturated hydrocarbons per gram organic carbon. Total organic carbon (TOC) content varies between 1.23 and 4.13 wt. %, depending on the purity of the sample, with the lowest values reflecting an increased contribution of skeletal debris to the ooids. Total organic extract (TOE) values range from 550 to 650 ppm an show a slight transformation in the direction of oil formation. The organic matter isolated from ooids (termed protokerogen) is dominantly of algal facies. Elemental composition of this protokerogen showed mean atomic H/C, O/C, and N/C ratios of 1.76, 0.24, and 0.19, respectively. Following pyrolysis, CR/CT ratios were found to be very low, with a mean of 0.18. All the results, including a thermal alteration index (TAI) of 1 to 1.5 on Staplin's scale and a very strong green to blue-green fluorescence under ultraviolet light excitation, point toward an immature, high grade, kerogen-type material with enormous potential for generating hydrocarbons. Additional experiments using a high pressure cell to simulate diagenesis in the ooids showed profound changes in their organic geochemistry wi h the contained organic matter following the predicted evolution path for type II kerogen. There is strong evidence that with deeper burial and prolonged exposure to higher temperatures, and perhaps to catalytic influence of the clay minerals (0.05%) and traces of metals (e.g., Ti, Mn, Sr, V) found in ooids, the organic matter will generate significant amounts of hydrocarbons. In those oolites with a favorable history of porosity development, the hydrocarbons would migrate along the continuous groundmass of organic matter within the ooids and into the pore spaces to accumulate as petroleum. End_Page 486------------------------------ The indigenous origin of petroleum in oolites, which obviates a long and wasteful primary migration process, affords an explanation for the exceptionally rich petroleum accumulations in such reservoirs. It is proposed that with the exception of leached oolites with oomoldic porosity, other petroleum-bearing oolites could be viewed as integrated source-reservoir beds. The prolific oolite reservoirs of the Arab Formation in Saudi Arabia were selected as natural case studies and the result found to be consistent with the hypothesis. End_of_Article - Last_Page 487------------