Development of a modified SEDEX phosphorus speciation method for ancient rocks and modern iron-rich sediments

We report the development of a modified method for evaluating different reservoirs of sedimentary phosphorus (P) in ancient marine sedimentary rocks and in modern Fe-rich sediments. Utilising the existing SEDEX scheme for P partitioning in modern sediments, we initially demonstrate limitations in the application of the original scheme to sediments and rocks containing crystalline hematite and magnetite. We tested additional extractions for these crystalline Fe phases, using both synthetic minerals, and modern and ancient sediments. The addition of 6 h oxalate and 6 h citrate-dithionate-acetate extractions considerably enhanced the total recovery of synthetic magnetite and hematite to 88.7 ± 1.1% and 76.9 ± 3.8%, respectively. In addition, application of the 6 h oxalate extraction to synthetic P-containing magnetite recovered 93.9 ± 1.7% of the Fe present and 88.2 ± 12.8% of the co-precipitated P. Based upon these results we developed a modified SEDEX extraction scheme. The modified scheme was applied to modern Fe-rich sediments from Golfo Dulce, Costa Rica, which resulted in 16% higher Fe-bound P recovery. Application of the scheme to a variety of ancient marine rocks increased the recovery of Fe-bound P by up to 22%. We also highlight the potential for authigenic carbonate fluorapatite to convert to more crystalline apatite in ancient rocks during deep burial and metamorphism. We suggest that in such systems minimum and maximum estimates of the total reactive P pool may be calculated with and without the inclusion of crystalline P. It is noted that the application of the revised method may have important implications for understanding the cycling of P in ancient marine environments

Experimental investigation of flow-induced vibration of a rotating circular cylinder

While flow-induced vibration of bluff bodies has been extensively studied over the last half-century, only limited attention has been given to flow-induced vibration of elastically mounted rotating cylinders. Since recent low-Reynolds-number numerical work suggests that rotation can enhance or suppress the natural oscillatory response, the former could find applications in energy harvesting and the latter in vibration control. The present experimental investigation characterises the dynamic response and wake structure of a rotating circular cylinder undergoing vortex-induced vibration at a low mass ratio (m∗ = 5.78) over the reduced velocity range leading to strong oscillations. The experiments were conducted in a free-surface water channel with the cylinder vertically mounted and attached to a motor that provided constant rotation. Springs and an air-bearing system allow the cylinder to undertake low-damped transverse oscillations. Under cylinder rotation, the normalised frequency response was found to be comparable to that of a freely vibrating non-rotating cylinder. At reduced velocities consistent with the upper branch of a non-rotating transversely oscillating cylinder, the maximum oscillation amplitude increased with non-dimensional rotation rate up to α ≈ 2. Beyond this, there was a sharp decrease in amplitude. Notably, this critical value corresponds approximately to the rotation rate at which vortex shedding ceases for a non-oscillating rotating cylinder. Remarkably, at α = 2 there was approximately an 80% increase in the peak amplitude response compared to that of a non-rotating cylinder. The observed amplitude response measured over the Reynolds-number range of (1100 Re 6300) is significantly different from numerical predictions and other experimental results recorded at significantly lower Reynolds numbers

Experimental investigation of flow-induced vibration of a sinusoidally rotating circular cylinder

The present experimental investigation characterises the dynamic response and wake structure of a sinusoidally rotating circular cylinder with a low mass ratio (defined as the ratio of the total oscillating mass to the displaced fluid mass) undergoing cross-stream flow-induced vibration (FIV). The study covers a wide parameter space spanning the forcing rotary oscillation frequency ratio

Occurrence and assemblage composition of intertidal non-native species may be influenced by shipping patterns and artificial structures

Habitat modification coupled with the spread of non-native species (NNS) are among the top threats to marine biodiversity globally. Species are known to be transported to new locations via international shipping and secondarily spread via regional vessels and artificial structures. Rapid Assessment Surveys (RAS) combining quantitative and semi-quantitative methods compared NNS richness and assemblage composition on intertidal natural rocky shores and artificial structures in harbours in different regions along the south coast of England. Quantitative data showed that artificial habitats supported higher richness than natural habitats, while semi-quantitative data found no difference in richness among habitat types. This result was attributed to additional species found in rock pools during searches of complex microhabitats in natural habitats. Assemblages on artificial structures differed among regions, with regions and harbours with greater numbers of vessels supporting greater richness. Results highlight the importance of shipping and artificial structures for NNS introduction and spread

Magnetar-like X-ray Bursts from an Anomalous X-ray Pulsar

Anomalous X-ray Pulsars (AXPs) are a class of rare X-ray pulsars whose energy source has been perplexing for some 20 years. Unlike other, better understood X-ray pulsars, AXPs cannot be powered by rotation or by accretion from a binary companion, hence the designation ``anomalous.'' AXP rotational and radiative properties are strikingly similar to those of another class of exotic objects, the Soft Gamma Repeaters (SGRs). However, the defining property of SGRs, namely their low-energy gamma-ray and X-ray bursts, have heretofore not been seen in AXPs. SGRs are thought to be ``magnetars,'' young neutron stars powered by the decay of an ultra-high magnetic field. The suggestion that AXPs are magnetars has been controversial. Here we report the discovery, from the direction of AXP 1E 1048-5937, of two X-ray bursts that have many properties similar to those of SGR bursts. These events imply a close relationship between AXPs and SGRs, with both being magnetars.Comment: 14 pages, 2 figures, accepted for publication in Nature. Note: The content of this paper is embargoed until 1900 hrs London time / 1400 US Eastern Time on Sept 1

Stereospecific decarboylative allylation of sulfones

This document is the Accepted Manuscript version of a Published Work that appeared in final form in the Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://doi.org/10.1021/ja104196x.Allyl sulfonyl acetic esters undergo highly stereospecific, palladium-catalyzed decarboxylative allylation. The reaction allows the stereospecific formation of tertiary homoallylic sulfones in high yield. In contrast to related reactions that proceed at -100 °C and require highly basic preformed organometallics, the decarboxylative coupling described herein occurs under mild non-basic conditions and requires no stoichiometric additives. Allylation of the intermediate α-sulfonyl anion is more rapid than racemization, leading to a highly enantiospecific process. DFT calculations indicate that the barrier for racemization is 9.9 kcal/mol and thus the barrier of allylation must be <9.9 kcal/mol

Morphologic and Biochemical Changes in Dogs After Portacaval Shunt Plus Bile Fistula or Ileal Bypass: Failure of Bile Fistula or Ileal Bypass to Prevent Hepatocyte Atrophy

External biliary fistula (BF) or ileal bypass (IB) was performed in dogs at the time of or 2 weeks after portacaval shunt (PCS). The pathologic changes in the dog livers 2 to 4 weeks later were compared to those caused by PCS alone. Histopathologic differences between PCS alone vs. PCS plus BF or IB could not be found. Thus, the experiments did not confirm recent observations by others in rats that BF prevents or reverses the hepatic injury of PCS. As estimated by plasma mevalonic acid determinations, the increase in hepatic cholesterol synthesis that is characteristic after BF or IB was suppressed in animals with PCS. BF and IB reduced but did not eliminate the postprandial elevation in serum bile acid that occurs after PCS. The findings have possible relevance in planning the treatment of patients with familial hypercholesterolemia with the combined use of PCS and IB. Copyright © 1983 American Association for the Study of Liver Disease

Fetal Sex and RHD Genotyping with Digital PCR Demonstrates Greater Sensitivity than Real-time PCR.

BACKGROUND: Noninvasive genotyping of fetal RHD (Rh blood group, D antigen) can prevent the unnecessary administration of prophylactic anti-D to women carrying RHD-negative fetuses. We evaluated laboratory methods for such genotyping. METHODS: Blood samples were collected in EDTA tubes and Streck® Cell-Free DNA™ blood collection tubes (Streck BCTs) from RHD-negative women (n = 46). Using Y-specific and RHD-specific targets, we investigated variation in the cell-free fetal DNA (cffDNA) fraction and determined the sensitivity achieved for optimal and suboptimal samples with a novel Droplet Digital™ PCR (ddPCR) platform compared with real-time quantitative PCR (qPCR). RESULTS: The cffDNA fraction was significantly larger for samples collected in Streck BCTs compared with samples collected in EDTA tubes (P < 0.001). In samples expressing optimal cffDNA fractions (≥4%), both qPCR and digital PCR (dPCR) showed 100% sensitivity for the TSPY1 (testis-specific protein, Y-linked 1) and RHD7 (RHD exon 7) assays. Although dPCR also had 100% sensitivity for RHD5 (RHD exon 5), qPCR had reduced sensitivity (83%) for this target. For samples expressing suboptimal cffDNA fractions (<2%), dPCR achieved 100% sensitivity for all assays, whereas qPCR achieved 100% sensitivity only for the TSPY1 (multicopy target) assay. CONCLUSIONS: qPCR was not found to be an effective tool for RHD genotyping in suboptimal samples (<2% cffDNA). However, when testing the same suboptimal samples on the same day by dPCR, 100% sensitivity was achieved for both fetal sex determination and RHD genotyping. Use of dPCR for identification of fetal specific markers can reduce the occurrence of false-negative and inconclusive results, particularly when samples express high levels of background maternal cell-free DNA

The Exchange Rate and US Tourism Balance of Trade

This paper investigates evidence on the effect of dollar depreciation on the US tourism balance of trade. Export revenue and import spending functions are estimated separately with structural vector autoregressive methods to better capture the dynamic adjustment to exchange rate shocks. Quarterly data cover the period of floating exchange rates from 1973 through 2007. Depreciation raises long term US export revenue but there is no effect on import spending

The Exchange Rate and US Tourism Balance of Trade

This paper investigates evidence on the effect of dollar depreciation on the US tourism balance of trade. Export revenue and import spending functions are estimated separately with structural vector autoregressive methods to better capture the dynamic adjustment to exchange rate shocks. Quarterly data cover the period of floating exchange rates from 1973 through 2007. Depreciation raises long term US export revenue but there is no effect on import spending