Petroleum generation kinetics: Single versus multiple heating- ramp open-system pyrolysis

A B S T R A C T Some recent publications promote one-run, open-system pyrolysis experiments using a single heating rate (ramp) and fixed frequency factor to determine the petroleum generation kinetics of source-rock samples because, compared to multiple-ramp experiments, the method is faster, less expensive, and presumably yields similar results. Some one-ramp pyrolysis experiments yield kinetic results similar to those from multiple-ramp experiments. However, our data for 52 worldwide source rocks containing types I, II, IIS, II/III, and III kerogen illustrate that one-ramp kinetics introduce the potential for significant error that can be avoided by using high-quality kinetic measurements and multiple-ramp experiments in which the frequency factor is optimized by the kinetic software rather than fixed at some universal value. The data show that kinetic modeling based on a discrete activation energy distribution and three different pyrolysis temperature ramps closely approximates that determined from additional runs, provided the three ramps span an appropriate range of heating rates. For some source rocks containing well-preserved kerogen and having narrow activation energy distributions, both single-and multiple-ramp discrete models are insufficient, and nucleation-growth models are necessary. Instrument design, thermocouple size or orientation, and sample weight likely influence the acceptable upper limit of pyrolysis heating rate. Caution is needed for ramps of 30-50°C/min, which can cause temperature errors due to impaired heat transfer between the oven, sample, and thermocouple. Compound volatility may inhibit pyrolyzate yield at the lowest heating rates, depending on the effectiveness of the gas sweep. We recommend at least three pyrolysis ramps that span at least a 20-fold variation of comparatively lower rates, such as 1, 5, and 25°C/min. The product of heating rate an

The future of North American trade policy: lessons from NAFTA

This repository item contains a single issue of the Pardee Center Task Force Reports, a publication series that began publishing in 2009 by the Boston University Frederick S. Pardee Center for the Study of the Longer-Range Future.This Task Force Report written by an international group of trade policy experts calls for significant reforms to address adverse economic, environmental, labor and societal impacts created by the 1994 North American Free Trade Agreement (NAFTA). The report is intended to contribute to the discussion and decisions stemming from ongoing reviews of proposed reforms to NAFTA as well as to help shape future trade agreements. It offers detailed proposals on topics including services, manufacturing, agriculture, investment, intellectual property, labor, environment, and migration. Fifteen years after NAFTA was enacted, there is widespread agreement that the trade treaty among the United States, Canada and Mexico has fallen short of its stated goals. While proponents credit the agreement with stimulating the flow of goods, services, and investment among the North American countries, critics in all three countries argue that this has not brought improvements in the standards of living of most people. Rather than triggering a convergence across the three nations, NAFTA has accentuated the economic and regulatory asymmetries that had existed among the three countries. [TRUNCATED

Modelling Cognitive Decline in the Hypertension in the Very Elderly Trial [HYVET] and Proposed Risk Tables for Population Use

Although, on average, cognition declines with age, cognition in older adults is a dynamic process. Hypertension is associated with greater decline in cognition with age, but whether treatment of hypertension affects this is uncertain. Here, we modelled dynamics of cognition in relation to the treatment of hypertension, to see if treatment effects might better be discerned by a model that included baseline measures of cognition and consequent mortalityThis is a secondary analysis of the Hypertension in the Very Elderly Trial (HYVET), a double blind, placebo controlled trial of indapamide, with or without perindopril, in people aged 80+ years at enrollment. Cognitive states were defined in relation to errors on the Mini-Mental State Examination, with more errors signifying worse cognition. Change in cognitive state was evaluated using a dynamic model of cognitive transition. In the model, the probabilities of transitions between cognitive states is represented by a Poisson distribution, with the Poisson mean dependent on the baseline cognitive state. The dynamic model of cognitive transition was good (R(2) = 0.74) both for those on placebo and (0.86) for those on active treatment. The probability of maintaining cognitive function, based on baseline function, was slightly higher in the actively treated group (e.g., for those with the fewest baseline errors, the chance of staying in that state was 63% for those on treatment, compared with 60% for those on placebo). Outcomes at two and four years could be predicted based on the initial state and treatment.A dynamic model of cognition that allows all outcomes (cognitive worsening, stability improvement or death) to be categorized simultaneously detected small but consistent differences between treatment and control groups (in favour of treatment) amongst very elderly people treated for hypertension. The model showed good fit, and suggests that most change in cognition in very elderly people is small, and depends on their baseline state and on treatment. Additional work is needed to understand whether this modelling approach is well suited to the valuation of small effects, especially in the face of mortality differences between treatment groups.ClinicalTrials.gov NCT0012281

Sulfur speciation in heavy petroleums: Information from X-ray absorption near-edge structure

The chemical speciation of sulfur in heavy petroleums, petroleum source rock extracts, and source rock pyrolysis products was studied using X-ray absorption near-edge structure (XANES) spectroscopy. The good energy resolution (ca. 0.5 eV) at the sulfur K edge and the strong dependence of XANES on the sulfur environment combine to give excellent sensitivity to changes in the electronic and structural environment of the sulfur. This has permitted identification and approximate quantitation of different classes of sulfur-containing compounds (e.g., sulfur, sulfides (including disulfides and polysulfides as a group), thiophenes, sulfoxides, sulfones, sulfinic acids, sulfonic acids, and sulfate) in a series of petroleums and petroleum source rocks. Our results indicate that the sulfur speciation of geological samples can be correlated with differences in source depositional environment, thermal maturity, and aromaticity. We report organosulfur compositions for the asphaltene, maltene, and liquid Chromatographie fractions of two sulfur-rich oils. In addition, we find that the organosulfur species in some, but not all, oils are subject to oxidation upon storage and thus may also be susceptible to oxidation in shallow reservoirs exposed to oxic waters. This work illustrates the utility of XANES as a direct spectroscopic probe for the quantitative determination of sulfur species in geological samples.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/29445/1/0000527.pd

Global distribution of two fungal pathogens threatening endangered sea turtles

This work was supported by grants of Ministerio de Ciencia e Innovación, Spain (CGL2009-10032, CGL2012-32934). J.M.S.R was supported by PhD fellowship of the CSIC (JAEPre 0901804). The Natural Environment Research Council and the Biotechnology and Biological Sciences Research Council supported P.V.W. The funders had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript. Thanks Machalilla National Park in Ecuador, Pacuare Nature Reserve in Costa Rica, Foundations Natura 2000 in Cape Verde and Equilibrio Azul in Ecuador, Dr. Jesus Muñoz, Dr. Ian Bell, Dr. Juan Patiño for help and technical support during samplingPeer reviewedPublisher PD

Integrating comprehensive two-dimensional gas chromatography and downhole fluid analysis to validate a spill-fill sequence of reservoirs with variations of biodegradation, water washing and thermal maturity

Author Posting. © The Author(s), 2016. This is the author's version of the work. It is posted here for personal use, not for redistribution. The definitive version was published in Fuel 191 (2017): 538-554, doi:10.1016/j.fuel.2016.11.081.Optimization of crude oil production depends heavily on crude oil composition and its variation within individual reservoirs and across multiple reservoirs. In particular, asphaltene content has an enormous impact on crude oil viscosity and even the economic value of the fluids in the reservoir. Thus, it is highly desirable to understand the primary controls on crude oil composition and asphaltene distributions in reservoirs. Here, a complex oilfield in the North Sea containing six separate reservoirs is addressed. The crude oil is believed to have spilled out of deeper reservoirs into shallower reservoirs during the overall reservoir charging process. Asphaltene content is measured in-situ through downhole fluid analysis and is generally consistent with a spill-fill sequence in reservoir charging. Detailed compositional analysis of crude oil samples by comprehensive two-dimensional gas chromatography (GC×GC) is used to determine the extent and variation among the reservoirs of water washing, biodegradation and thermal maturity. Increased biodegradation and water washing in the shallower reservoirs is consistent with a spill-fill sequence. The water washing is evidently assisted by biodegradation. Moreover, analyses of four thermal maturity biomarkers show that shallower reservoirs contain less mature oil, again consistent with a spill-fill sequence. The combination of DFA for bulk compositional analysis and GC×GC for detailed compositional analysis with geochemical interpretation is an effective tool for unraveling complex oilfield scenarios

A Case-Control Study of Hantavirus Pulmonary Syndrome during an Outbreak in the Southwestern United States

In May 1993, an outbreak of hantavirus pulmonary syndrome( HPS) occurred in the south-western United States. A case-control study determined risk factors for HPS. Seventeen case-patients were compared with 3 groups of controls: members of case-patient households( household controls), members of neighboring households( near controls), and members of randomly selected households ≥ 24 km away ( far controls). Investigators trapped more small rodents at case households than at near ( P = .03) or far control households( P = .02). After the number of small rodents was controlled for,case-patients were more likely than household controls to hand plow (odds ratio [OR], 12.3; 95% confidence interval [ CI], 1.1-143.0) or to clean feed storage areas (OR, 33.4; 95% CI, 1.7-666.0). Case-patients were more likely than near controls to plant( OR, 6.2; 95% CI, 1.1-34.0) and more likely than far controls to clean animal sheds( OR, 11.9;95% CI, 1.4-103.0). Peridomestic cleaning, agricultural activities, and an increased number of small rodents at the household were associated with HPS

Combining biomarker and bulk compositional gradient analysis to assess reservoir connectivity

Author Posting. © The Author(s), 2010. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Organic Geochemistry 41 (2010): 812-821, doi:10.1016/j.orggeochem.2010.05.003.Hydraulic connectivity of petroleum reservoirs represents one of the biggest uncertainties for both oil production and petroleum system studies. Here, a geochemical analysis involving bulk and detailed measures of crude oil composition is shown to constrain connectivity more tightly than is possible with conventional methods. Three crude oils collected from different depths in a single well exhibit large gradients in viscosity, density, and asphaltene content. Crude oil samples are collected with a wireline sampling tool providing samples from well‐defined locations and relatively free of contamination by drilling fluids; the known provenance of these samples minimizes uncertainties in the subsequent analysis. The detailed chemical composition of almost the entire crude oil is determined by use of comprehensive two‐dimensional gas chromatography (GC×GC) to interrogate the nonpolar fraction and negative ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT‐ICR MS) to interrogate the polar fraction. The simultaneous presence of 25‐ norhopanes and mildly altered normal and isoprenoid alkanes is detected, suggesting that the reservoir has experienced multiple charges and contains a mixture of oils biodegraded to different extents. The gradient in asphaltene concentration is explained by an equilibrium model considering only gravitational segregation of asphaltene nanoaggregates; this grading can be responsible for the observed variation in viscosity. Combining these analyses yields a consistent picture of a connected reservoir in which the observed viscosity variation originates from gravitational segregation of asphaltene nanoaggregates in a crude oil with high asphaltene concentration resulting from multiple charges, including one charge that suffered severe biodegradation. Observation of these gradients having appropriate magnitudes suggests good reservoir connectivity with greater confidence than is possible with traditional techniques alone.The mass spectrometry work was supported by the NSF Division of Materials Research through DMR‐06‐54118, and the State of Florida

A Case-Control Study of Hantavirus Pulmonary Syndrome during an Outbreak in the Southwestern United States

In May 1993, an outbreak of hantavirus pulmonary syndrome( HPS) occurred in the south-western United States. A case-control study determined risk factors for HPS. Seventeen case-patients were compared with 3 groups of controls: members of case-patient households( household controls), members of neighboring households( near controls), and members of randomly selected households ≥ 24 km away ( far controls). Investigators trapped more small rodents at case households than at near ( P = .03) or far control households( P = .02). After the number of small rodents was controlled for,case-patients were more likely than household controls to hand plow (odds ratio [OR], 12.3; 95% confidence interval [ CI], 1.1-143.0) or to clean feed storage areas (OR, 33.4; 95% CI, 1.7-666.0). Case-patients were more likely than near controls to plant( OR, 6.2; 95% CI, 1.1-34.0) and more likely than far controls to clean animal sheds( OR, 11.9;95% CI, 1.4-103.0). Peridomestic cleaning, agricultural activities, and an increased number of small rodents at the household were associated with HPS