New Marker of Colon Cancer Risk Associated with Heme Intake: 1,4-Dihydroxynonane Mercapturic Acid

Background: Red meat consumption is associated with an increased risk of colon cancer. Animal studies show that heme, found in red meat, promotes preneoplastic lesions in the colon, probably due to the oxidative properties of this compound. End products of lipid peroxidation, such as 4-hydroxynonenal metabolites or 8-iso-prostaglandin-F2 (8-iso-PGF2), could reflect this oxidative process and could be used as biomarkers of colon cancer risk associated with heme intake. Methods: We measured urinary excretion of 8-iso-PGF2 and 1,4-dihydroxynonane mercapturic acid (DHN-MA), the major urinary metabolite of 4-hydroxynonenal, in three studies. In a short-term and a carcinogenesis long-term animal study, we fed rats four different diets (control, chicken, beef, and blood sausage as a high heme diet). In a randomized crossover human study, four different diets were fed (a 60 g/d red meat baseline diet, 120 g/d red meat, baseline diet supplemented with heme iron, and baseline diet supplemented with non-heme iron). Results: DHN-MA excretion increased dramatically in rats fed high heme diets, and the excretion paralleled the number of preneoplastic lesions in azoxymethane initiated rats (P < 0.0001). In the human study, the heme supplemented diet resulted in a 2-fold increase in DHN-MA (P < 0.001). Urinary 8-iso-PGF2 increased moderately in rats fed a high heme diet (P < 0.0001), but not in humans. Conclusion: Urinary DHN-MA is a useful noninvasive biomarker for determining the risk of preneoplastic lesions associated with heme iron consumption and should be further investigated as a potential biomarker of colon cancer risk. (Cancer Epidemiol Biomarkers Prev 2006;15(11):2274–9

Effect of Water Activity on Reaction Kinetics and Intergranular Transport: Insights from the Ca(OH) 2 + MgCO 3 → CaCO 3 + Mg(OH) 2 Reaction at 1·8 GPa

The kinetics of the irreversible reaction Ca(OH)2 + MgCO3 → CaCO3 + Mg(OH)2 were investigated at high pressures and temperatures relevant to metamorphic petrology, using both in situ synchrotron X-ray diffraction and post-mortem analysis of reaction rim growth on recovered samples. Reaction kinetics are found to strongly depend on water content; comparable bulk-reaction kinetics are obtained under water-saturated (excess water, c. 10 wt %) and under intermediate (0·1–1 wt % water) conditions when temperature is increased by c. 300 K. In contrast, similar reaction kinetics were observed at ∼673 K and 823 K between intermediate and dry experiments, respectively, where dry refers to a set of experiments with water activity below 1·0 (no free water), as buffered by the CaO–Ca(OH)2 assemblage. Given the activation energies at play, this gap—corresponding to the loss of no more than 1 wt % of water by the assemblage—leads to a difference of several orders of magnitude in reaction kinetics at a given temperature. Further analysis, at the microscopic scale, of the intermediate and dry condition samples, shows that intergranular transport of calcium controls the reaction progress. Grain boundary diffusivities could be retrieved from the classic treatment of reaction rim growth rate. In turn, once modeled, this rate was used to fit the bulk kinetic data derived from X-ray powder diffraction, offering an alternative means to derive calcium diffusivity data. Based on a comparison with effective grain boundary data for Ca and Mg from the literature, it is inferred that both dry and intermediate datasets are consistent with a water-saturated intergranular medium with different levels of connectivity. The very high diffusivity of Ca in the CaCO3 + Mg(OH)2 rims, in comparison with that of Mg in enstatite rims found by earlier workers, emphasizes the prominent role of the interactions between diffusing species and mineral surfaces in diffusion kinetics. Furthermore, we show that the addition of water is likely to change the relative diffusivity of Mg and Ca in carbonate aggregates. From a qualitative point of view, we confirm, in a carbonate-bearing system, that small water content variations within the 0–1 wt % range have tremendous effects on both intergranular transport mechanisms and kinetics. We also propose that the water content dependent diffusivity of major species (Mg, Ca) in low-porosity metamorphic rocks is strongly dependent on the interaction between diffusing species and mineral surfaces. This parameter, which will vary from one rock-type to another, needs also to considered when extrapolating (P, T, t, xH2O) laboratory diffusion data to metamorphic processes

Organics in comet 67P – a first comparative analysis of mass spectra from ROSINA–DFMS, COSAC and Ptolemy

The ESA Rosetta spacecraft followed comet 67P at a close distance for more than 2 yr. In addition, it deployed the lander Philae on to the surface of the comet. The (surface) composition of the comet is of great interest to understand the origin and evolution of comets. By combining measurements made on the comet itself and in the coma, we probe the nature of this surface material and compare it to remote sensing observations. We compare data from the double focusing mass spectrometer (DFMS) of the ROSINA experiment on ESA's Rosetta mission and previously published data from the two mass spectrometers COSAC (COmetary Sampling And Composition) and Ptolemy on the lander. The mass spectra of all three instruments show very similar patterns of mainly CHO-bearing molecules that sublimate at temperatures of 275 K. The DFMS data also show a great variety of CH-, CHN-, CHS-, CHO2- and CHNO-bearing saturated and unsaturated species. Methyl isocyanate, propanal and glycol aldehyde suggested by the earlier analysis of the measured COSAC spectrum could not be confirmed. The presence of polyoxymethylene in the Ptolemy spectrum was found to be unlikely. However, the signature of the aromatic compound toluene was identified in DFMS and Ptolemy data. Comparison with remote sensing instruments confirms the complex nature of the organics on the surface of 67P, which is much more diverse than anticipated

Spatial distribution of low-energy plasma around 2 comet 67P/CG from Rosetta measurements

International audienceWe use measurements from the Rosetta plasma consortium (RPC) Langmuir probe (LAP) and mutual impedance probe (MIP) to study the spatial distribution of low-energy plasma in the near-nucleus coma of comet 67P/Churyumov-Gerasimenko. The spatial distribution is highly structured with the highest density in the summer hemisphere and above the region connecting the two main lobes of the comet, i.e. the neck region. There is a clear correlation with the neutral density and the plasma to neutral density ratio is found to be ∼1-2·10 −6 , at a cometocentric distance of 10 km and at 3.1 AU from the sun. A clear 6.2 h modulation of the plasma is seen as the neck is exposed twice per rotation. The electron density of the collisonless plasma within 260 km from the nucleus falls of with radial distance as ∼1/r. The spatial structure indicates that local ionization of neutral gas is the dominant source of low-energy plasma around the comet

Atomically precise Au144(SR)60 nanoclusters (R = Et, Pr) are capped by 12 distinct ligand types of 5-fold equivalence and display gigantic diastereotopic effects

For two decades, Au144(SR)60 has been one of the most studied and used thiolate (SR) protected gold nanoclusters. In many ways, however, it proved to be a challenging and elusive case, also because of the difficulties in solving its structure by single-crystal X-ray crystallography. We used very short thiols and could prepare Au144(SC2H5)60 and Au144(SC3H7)60 in a very pure form, which was confirmed by UV-vis absorption spectroscopy and very regular electrochemistry patterns. Inductively coupled plasma and electrospray ionization mass spectrometries gave definite proof of the Au144(SR)60 stoichiometry. Highresolution 1D and 2D NMR spectroscopy in the solution phase provided the result of assessing the presence of 12 ligand types in exactly the same amount (5-fold equivalence). Equally important, we found that the two protons belonging to each methylene group along the thiolate chain are diastereotopic. For the a-CH2 protons, the diastereotopic effect can be indeed gigantic, as it reaches chemical-shift differences of 2.9 ppm. DFT calculations provided insights into the relationship between structure and NMR results. In particular, the 12 ligand types and corresponding diastereotopic effects may be explained by considering the presence of C\u2013H/S hydrogen bonds. These results thus provide fundamental insights into the structure of the thiolate layer capping this long-studied gold nanocluster

Biogeochemical aspects of bottom anoxia in a Mediterranean lagoon (Thau, France)

Physical and chemical characteristics (temperature, salinity, dissolved oxygen), nutrients [dissolved inorganic nitrogen (DIN), soluble reactive phosphorus (SRP) and silicate], dissolved organic nitrogen (DON) and phosphorus and particulate matter [particulate organic carbon (POC) and nitrogen (PON) and chlorophyll a] were measured at a station located in the deepest part of the Thau lagoon (8.5 m), France, during a 10 d period of bottom anoxia in summer 1994. The upper 8 cm of sediment were also analyzed for ammonium (NH(4)(+)) and SRP concentrations in the porewater. The study period was characterized by mean wind speed under 4 m s(-1) which induced an increase of surface temperature from 18 to 29 degrees C with the formation of a thermocline. The correlation (p < 10(-4)) between the wind speed averaged over the previous day and the difference between bottom and surface temperatures showed that the wind constituted the main vector of vertical mixing. The lack of wind led to dissolved oxygen depletion in the bottom 2 m and to a strong porosity increase in the upper 10 cm of sediment (80 to >95%). Anoxic conditions increased NH(4)(+) and SRP concentrations in porewater from 231 +/- 89 to 1305 +/- 305 (+/- SD) mu M and from 6.6 +/- 0.8 to 108 +/- 43 mu M respectively. The potential increase of NH(4)(+) concentrations in porewater estimated from the mineralization of the microphytobenthos explained 30% of the measured increase in the upper 8 cm of porewater. The study period was characterized by an increase in NH(4)(+) SRP and dissolved Si concentrations in the bottom water column (maxima respectively 24.2, 4.9 and 57 mu M). Linear regressions between nutrient concentrations in the water column and temperature revealed a strong enhancement of bottom fluxes during anoxia. Nitrate + nitrite (NO(3)(-) + NO(2)(-)) were absent in anoxic waters and remained below 0.5 mu M in oxic waters. Monthly concentrations of SRP in the water column of the Thau lagoon from 1970 to 1994 revealed anoxia events by summer peak values corresponding to strong bottom anoxia. Nevertheless, the general trend was a decrease due to the gradual control of eutrophication which should lead to the disappearance of bottom anoxia within the next decade. A fraction of the nutrients of benthic origin was transformed into planktonic particulate matter via primary production which increased the concentrations of chi a from about 1 to 15 mu g l(-1). Concentrations of DON and PON in the water column were significantly correlated, suggesting that DON compounds were released by the pelagic food web but not directly by the sediment. The increase of total nitrogen (DIN + DON + PON), considering the water column as a closed box during 10 d of winds under 5 m s(-1), was estimated at 1.7 mu mol N l(-1) d(-1) and would correspond to a benthic flux of 600 mu mol N m(-1) h(-1) for 10 d

Solar wind sputtering of dust on the surface of 67P/Churyumov-Gerasimenko

International audienceFar away from the Sun, at around 3 AU, the activity of comet 67P/Churyumov-Gerasimenko is low and changes with local time (solar insolation), with location (chemical heterogeneity of the surface), and with season. When the activity is very low because the total cross section of the comet against the Sun is small, the solar wind has access to the surface of the comet and causes ion-induced sputtering of surface material, which we wish to observe.Methods. We used the Double Focussing Mass Spectrometer (DFMS) of the ROSINA experiment on ESA’s Rosetta mission to search for mass spectrometric evidence of sputtered refractory species. In high-resolution mode, DFMS can separate some of the mass peaks of refractory elements from the many volatile species present in the coma.Results. At present, the locations of solar wind surface access are in the southern hemisphere of the comet (the local winter). Of particular interest is sputtering of dust grains on the surface. We observe global averages over the winter hemisphere of the refractory elements Na, K, Si, and Ca, presumably sputtered from grains residing on the surface. Compared to carbonaceous chondrites, the comet has the same Na abundance, is depleted in Ca, and has an excess of K. In addition, for Si the signal strength is strong enough to compile a coarse compositional map of the southern hemisphere. Most, perhaps all, of the observed variation can be explained by the solar wind being affected by the atmosphere of the comet