Polycyclic aromatic hydrocarbons and petroleum biomarkers in Sao Sebastiao Channel, Brazil: Assessment of petroleum contamination

Polycyclic aromatic hydrocarbons (PAHs) and non-aromatic hydrocarbons (NAHs), including n-alkanes, isoprenoids and petroleum biomarkers (terpanes, hopanes, steranes and diasteranes), were quantified by gas chromatography with flame ionization and mass spectrometer detectors in sediment samples collected from the Sao Sebastiao Channel (SSC), Brazil, where the largest Brazilian maritime petroleum terminal is located The concentrations of total PAHs. total n-alkanes and petroleum biomarkers ranged from below the detection limits to 370 ng g(-1,) 28 mu g g(-1), 2200 ng g(-1) (dry weight), respectively. The analysis of PAN distribution suggested combustion sources of PAHs as the main input for these compounds with smaller amount from petroleum contamination The distribution of petroleum biomarkers undoubtedly demonstrated petroleum as a source of anthropogenic contamination throughout the region. The assessment of petrogenic sources of contamination in marine sediment is more challenging if only PAH analysis were carried out, which demonstrates that more stable hydrocarbons such as petroleum biomarkers are useful for investigating potential presence of petroleum (C) 2009 Elsevier Ltd. All rights reserved.

Processos naturais de biodegradação do petróleo em reservatórios

Petroleum biodegradation in reservoirs is a process caused by different microorganisms affecting many oil deposits which modifies the oil composition in a quasi-stepwise process starting from n-alkanes and isoprenoids through to diasteranes. This causes oil souring and increased viscosity, sulfur and metal content, having a direct impact on oil production and refining costs.

Processos naturais de biodegradação do petróleo em reservatórios

Petroleum biodegradation in reservoirs is a process caused by different microorganisms affecting many oil deposits which modifies the oil composition in a quasi-stepwise process starting from n-alkanes and isoprenoids through to diasteranes. This causes oil souring and increased viscosity, sulfur and metal content, having a direct impact on oil production and refining costs.

Evaluation of exposure biomarkers in offshore workers exposed to low benzene and toluene concentrations.

Characterize ethylbenzene and xylene air concentrations, and explore the biological exposure markers (urinary t,t-muconic acid (t,t-MA) and unmetabolized toluene) among petroleum workers offshore. Offshore workers have increased health risks due to simultaneous exposures to several hydrocarbons present in crude oil. We discuss the pooled benzene exposure results from our previous and current studies and possible co-exposure interactions. BTEX air concentrations were measured during three consecutive 12-h work shifts among 10 tank workers, 15 process operators, and 18 controls. Biological samples were collected pre-shift on the first day of study and post-shift on the third day of the study. The geometric mean exposure over the three work shifts were 0.02 ppm benzene, 0.05 ppm toluene, 0.03 ppm ethylbenzene, and 0.06 ppm xylene. Benzene in air was significantly correlated with unmetabolized benzene in blood (r = 0.69, p < 0.001) and urine (r = 0.64, p < 0.001), but not with urinary t,t-MA (r = 0.27, p = 0.20). Toluene in air was highly correlated with the internal dose of toluene in both blood (r = 0.70, p < 0.001) and urine (r = 0.73, p < 0.001). Co-exposures were present; however, an interaction of metabolism was not likely at these low benzene and toluene exposures. Urinary benzene, but not t,t-MA, was a reliable biomarker for benzene at low exposure levels. Urinary toluene was a useful biomarker for toluene exposure. Xylene and ethylbenzene air levels were low. Dermal exposure assessment needs to be performed in future studies among these workers.

Evidence for euphotic zone anoxia during the deposition of Aptian source rocks based on aryl isoprenoids in petroleum, Sergipe-Alagoas Basin, northeastern Brazil

Four crude oil samples from the Sergipe-Alagoas Basin, northeastern Brazil, were analyzed using full scan gas chromatography-quadrupole mass spectrometry (GC-qMS) for biomarkers, in order to correlate them using aromatic carotenoids thereby enhancing knowledge about the depositional environment of their source rocks. The geochemical parameters derived from saturated fractions of the oils show evidence of little or no biodegradation and similar thermal maturation (Ts/(Ts+Tm) for terpanes, C29 αββ/(αββ+ααα), C27, and C29 20S/(20S+20R) for steranes). Low pristane/phytane ratios and the abundance of gammacerane and β-carotane are indicative of an anoxic and saline depositional environment for the source rocks. Moreover, we identified a large range of diagenetic and catagenetic products of the aromatic carotenoid isorenieratene, including C40, C33, and C32 diaryl isoprenoids and aryl isoprenoid derivatives with short side chains and/or additional rings. These results indicate anoxia in the photic zone during the deposition of the source rocks. © 2013 The Authors.

Phylogenetic Analysis Of The Microbial Community In Hypersaline Petroleum Produced Water From The Campos Basin.

In this work the archaea and eubacteria community of a hypersaline produced water from the Campos Basin that had been transported and discharged to an onshore storage facility was evaluated by 16S recombinant RNA (rRNA) gene sequence analysis. The produced water had a hypersaline salt content of 10 (w/v), had a carbon oxygen demand (COD) of 4,300 mg/l and contains phenol and other aromatic compounds. The high salt and COD content and the presence of toxic phenolic compounds present a problem for conventional discharge to open seawater. In previous studies, we demonstrated that the COD and phenolic content could be largely removed under aerobic conditions, without dilution, by either addition of phenol degrading Haloarchaea or the addition of nutrients alone. In this study our goal was to characterize the microbial community to gain further insight into the persistence of reservoir community members in the produced water and the potential for bioremediation of COD and toxic contaminants. Members of the archaea community were consistent with previously identified communities from mesothermic reservoirs. All identified archaea were located within the phylum Euryarchaeota, with 98 % being identified as methanogens while 2 % could not be affiliated with any known genus. Of the identified archaea, 37 % were identified as members of the strictly carbon-dioxide-reducing genus Methanoplanus and 59 % as members of the acetoclastic genus Methanosaeta. No Haloarchaea were detected, consistent with the need to add these organisms for COD and aromatic removal. Marinobacter and Halomonas dominated the eubacterial community. The presence of these genera is consistent with the ability to stimulate COD and aromatic removal with nutrient addition. In addition, anaerobic members of the phyla Thermotogae, Firmicutes, and unclassified eubacteria were identified and may represent reservoir organisms associated with the conversion hydrocarbons to methane.

Genome Sequence Of Bacillus Safensis Cfa06, Isolated From Biodegraded Petroleum In Brazil.

Bacillus safensis is a microorganism recognized for its biotechnological and industrial potential due to its interesting enzymatic portfolio. Here, as a means of gathering information about the importance of this species in oil biodegradation, we report a draft genome sequence of a strain isolated from petroleum.

The Effect Of Soy Dietary Supplement And Low Dose Of Hormone Therapy On Main Cardiovascular Health Biomarkers: A Randomized Controlled Trial.

To assess the effects of a soy dietary supplement on the main biomarkers of cardiovascular health in postmenopausal women compared with the effects of low-dose hormone therapy (HT) and placebo. Double-blind, randomized and controlled intention-to-treat trial. Sixty healthy postmenopausal women, aged 40-60 years, 4.1 years mean time since menopause were recruited and randomly assigned to 3 groups: a soy dietary supplement group (isoflavone 90mg), a low-dose HT group (estradiol 1 mg plus noretisterone 0.5 mg) and a placebo group. Lipid profile, glucose level, body mass index, blood pressure and abdominal/hip ratio were evaluated in all the participants at baseline and after 16 weeks. Statistical analyses were performed using the χ2 test, Fisher's exact test, Kruskal-Wallis non-parametric test, analysis of variance (ANOVA), paired Student's t-test and Wilcoxon test. After a 16-week intervention period, total cholesterol decreased 11.3% and LDL-cholesterol decreased 18.6% in the HT group, but both did not change in the soy dietary supplement and placebo groups. Values for triglycerides, HDL-cholesterol, glucose level, body mass index, blood pressure and abdominal/hip ratio did not change over time in any of the three groups. The use of dietary soy supplement did not show any significant favorable effect on cardiovascular health biomarkers compared with HT. The trial is registered at the Brazilian Clinical Trials Registry (Registro Brasileiro de Ensaios Clínicos - ReBEC), number RBR-76mm75.

Whole Cortical And Default Mode Network Mean Functional Connectivity As Potential Biomarkers For Mild Alzheimer's Disease.

The search for an Alzheimer's disease (AD) biomarker is one of the most relevant contemporary research topics due to the high prevalence and social costs of the disease. Functional connectivity (FC) of the default mode network (DMN) is a plausible candidate for such a biomarker. We evaluated 22 patients with mild AD and 26 age- and gender-matched healthy controls. All subjects underwent resting functional magnetic resonance imaging (fMRI) in a 3.0 T scanner. To identify the DMN, seed-based FC of the posterior cingulate was calculated. We also measured the sensitivity/specificity of the method, and verified a correlation with cognitive performance. We found a significant difference between patients with mild AD and controls in average z-scores: DMN, whole cortical positive (WCP) and absolute values. DMN individual values showed a sensitivity of 77.3% and specificity of 70%. DMN and WCP values were correlated to global cognition and episodic memory performance. We showed that individual measures of DMN connectivity could be considered a promising method to differentiate AD, even at an early phase, from normal aging. Further studies with larger numbers of participants, as well as validation of normal values, are needed for more definitive conclusions.

Bioremediation Potential Of Microorganisms Derived From Petroleum Reservoirs.

Bacterial strains and metagenomic clones, both obtained from petroleum reservoirs, were evaluated for petroleum degradation abilities either individually or in pools using seawater microcosms for 21 days. Gas Chromatography-Flame Ionization Detector (GC-FID) and Gas Chromatography-Mass Spectrometry (GC-MS) analyses were carried out to evaluate crude oil degradation. The results showed that metagenomic clones 1A and 2B were able to biodegrade n-alkanes (C14 to C33) and isoprenoids (phytane and pristane), with rates ranging from 31% to 47%, respectively. The bacteria Dietzia maris CBMAI 705 and Micrococcus sp. CBMAI 636 showed higher rates reaching 99% after 21 days. The metagenomic clone pool biodegraded these compounds at rates ranging from 11% to 45%. Regarding aromatic compound biodegradation, metagenomic clones 2B and 10A were able to biodegrade up to 94% of phenanthrene and methylphenanthrenes (3-MP, 2-MP, 9-MP and 1-MP) with rates ranging from 55% to 70% after 21 days, while the bacteria Dietzia maris CBMAI 705 and Micrococcus sp. CBMAI 636 were able to biodegrade 63% and up to 99% of phenanthrene, respectively, and methylphenanthrenes (3-MP, 2-MP, 9-MP and 1-MP) with rates ranging from 23% to 99% after 21 days. In this work, isolated strains as well as metagenomic clones were capable of degrading several petroleum compounds, revealing an innovative strategy and a great potential for further biotechnological and bioremediation applications.

Increased Arterial Stiffness In Resistant Hypertension Is Associated With Inflammatory Biomarkers.

Increased levels of inflammatory biomarkers such as interleukin-6 (IL-6), 10 (IL-10), 1β (IL-1β), tumor necrosis factor-α (TNF-α) high-sensitivity C-reactive protein (hs-CRP) are associated with arterial stiffness in hypertension. Indeed, resistant hypertension (RHTN) leads to unfavorable prognosis attributed to poor blood pressure (BP) control and target organ damage. This study evaluated the potential impact of inflammatory biomarkers on arterial stiffness in RHTN. In this cross-sectional study, 32 RHTN, 20 mild hypertensive (HTN) and 20 normotensive (NT) patients were subjected to office BP and arterial stiffness measurements assessed by pulse wave velocity (PWV). Inflammatory biomarkers were measured in plasma samples. PWV was increased in RHTN compared with HTN and NT (p < 0.05). TNF-α levels were significantly higher in RHTN and HTN than NT patients. No differences in IL-6 levels were observed. RHTN patients had a higher frequency of subjects with increased levels of IL-10 and IL-1β compared with HTN and NT patients. Finally, IL-1β was independently associated with PWV (p < 0.001; R(2) = 0.5; β = 0.077). RHTN subjects have higher levels of inflammatory cytokines (TNF-α, IL-1β and IL-10) as well as increased arterial stiffness, and detectable IL-1β levels are associated arterial stiffness. These findings suggest that inflammation plays a possible role in the pathophysiology of RHTN.

Assessment Of Sleep Bruxism, Orthodontic Treatment Need, Orofacial Dysfunctions And Salivary Biomarkers In Asthmatic Children.

To evaluate the sleep bruxism, malocclusions, orofacial dysfunctions and salivary levels of cortisol and alpha-amylase in asthmatic children. 108 7-9-yr-old children were selected from Policlinic Santa Teresinha Doutor Antonio Haddad Dib (asthmatics, n=53) and from public schools (controls, n=55), Piracicaba, SP, Brazil. Sleep bruxism diagnosis was confirmed by parental report of grinding sounds and the presence of shiny and polish facets on incisors and/or first permanent molars. The index of orthodontic treatment need was used for occlusion evaluation. Orofacial dysfunctions were evaluated using the nordic orofacial test-screening (NOT-S). Salivary cortisol and alpha-amylase were expressed as awakening response (AR), calculated as the difference between levels immediately after awakening and 30min after waking, and diurnal decline (DD), calculated as the difference between levels at 30min after waking and at bedtime. Data were analyzed using Shapiro-Wilk/Kolmogorov-Smirnov, Chi-square, unpaired t test/Mann-Whitney and paired t/Wilcoxon tests. Sleep bruxism was more prevalent in children with asthma than controls (47.2% vs. 27.3%, p<0.05). Asthmatics had higher scores of NOT-S total and interview (p<0.05). Dysfunctions on sensory function and chewing and swallowing were more frequent in asthmatics (p<0.05). Salivary cortisol AR on weekend was significantly higher for asthmatics (p<0.05). Salivary cortisol DD was significantly higher on weekday than weekend for controls (p<0.05). There were no significant differences in alpha-amylase values in and between groups. The presence of asthma in children was associated with sleep bruxism, negative perception of sensory, chewing and swallowing functions, and higher concentrations of salivary cortisol on weekend.

PAH biomarkers for human health risk assessment: a review of the state-of-the-art

Polycyclic aromatic hydrocarbons (PAH) are widely distributed in the environment, and some are carcinogenic to human beings. The study of biomarkers has helped clarify the nature and magnitude of the human health risks posed by such substances. This article provides a review of the state-of-the-art on PAH biomarkers for human health risk assessment and also discusses their applicability within the context of environmental management in Brazil. The article discusses the methodologies for determination of some biomarkers such as 1-hydroxypyrene and PAH-DNA adducts. Cytogenetic markers, frequency of chromosomal aberrations, and micronucleus induction were considered for the evaluation of cancer risk. The current stage of studies on validation of such biomarkers was also approached.

Biomass Refinery as a Renewable Complement to the Petroleum Refinery

Biomass Refinery is a sequential of eleven thermochemical processes and one biological process with two initial basic treatments: prehydrolysis for lignocellulosics and low temperature conversion for biomass with medium-to-high content of lipids and proteins. The other ten processes are: effluent treatment plant, furfural plant, biodiesel plant, cellulignin dryer, calcination, fluidized bed boiler, authotermal reforming of cellulignin for syngas production, combined cycle of two-stroke low-speed engine or syngas turbine with fluidized bed boiler heat recovery, GTL technologies and ethanol from cellulose, prehydrolysate and syngas. Any kind of biomass such as wood, agricultural residues, municipal solid waste, seeds, cakes, sludges, excrements and used tires can be processed at the Biomass Refinery. Twelve basic products are generated such as cellulignin, animal feed, electric energy, fuels (ethanol, crude oil, biodiesel, char), petrochemical substitutes, some materials (ash, gypsum, fertilizers, silica, carbon black) and hydrogen. The technology is clean with recovery of energy and reuse of water, acid and effluents. Based on a holistic integration of various disciplines Biomass Refinery maximizes the simultaneous production of food, electric energy, liquid fuels and chemical products and some materials, achieving a competitive position with conventional and fossil fuel technologies, as well as payment capacity for biomass production. Biomass Refinery has a technical economical capability to complement the depletion of the conventional petroleum sources and to capture its GHGs resulting a biomass + petroleum ""green"" combination.