In situ laser heating and radial synchrotron x-ray diffraction in a diamond anvil cell

We report a first combination of diamond anvil cell radial x-ray diffraction with in situ laser heating. The laser-heating setup of ALS beamline 12.2.2 was modified to allow one-sided heating of a sample in a diamond anvil cell with an 80 W yttrium lithium fluoride laser while probing the sample with radial x-ray diffraction. The diamond anvil cell is placed with its compressional axis vertical, and perpendicular to the beam. The laser beam is focused onto the sample from the top while the sample is probed with hard x-rays through an x-ray transparent boron-epoxy gasket. The temperature response of preferred orientation of (Fe,Mg)O is probed as a test experiment. Recrystallization was observed above 1500 K, accompanied by a decrease in stress.     

Behavior of the polycyclic musks HHCB and AHTN in lakes, two potential anthropogenic markers for domestic wastewater in surface waters

The synthetic polycyclic musks HHCB and AHTN are potential chemical markers for domestic wastewater contamination of surface waters. Understanding their environmental behavior is important to evaluate their suitability as markers. This study focuses on the quantification of the processes that lead to an elimination in lakes. Rate constants for all relevant processes were estimated based on laboratory studies and models previously described. In lake Zurich, during winter time, both compounds are eliminated primarily by outflowing water and due to losses to the atmosphere. In summer, direct photolysis represents the predominant elimination process for AHTN in the epilimnion of lake Zurich (quantum yield, 0.12), whereas for HHCB, photochemical degradation is still negligible. HHCB and AHTN were then measured in effluents of Swiss wastewater treatment plants (WWTPs), in remote and anthropogenically influenced Swiss surface waters, and in Mediterranean seawater using an analytical procedure based on SPE and GC-MS-SIM with D6-HHCB as internal standard (LODs for natural waters, 2 and 1 ng/L, respectively). In winter, concentrations of HHCB and AHTN in lakes (<2-47 and <1-18 ng/L, respectively) correlated with the anthropogenic burden by domestic wastewater (ratio population per water throughflow), demonstrating the suitability of these compounds as quantitative, source-specific markers. In summer, however, no such correlations were observed. Vertical concentration profiles in lake Zurich indicated significant losses in the epilimnion during summer, mainly for AHTN, and could be rationalized with a lake modeling program (MASASlight), considering measured, average loads from WWTP effluents (0.80 +/- 0.22 and 0.32 +/- 0.11 mg person(-1) d(-1) for HHCB and AHTN, respectively) and the estimated rate constants for elimination processes.     

Environmental behavior of the chiral acetamide pesticide metalaxyl: enantioselective degradation and chiral stability in soil

Racemic metalaxyl is currently being replaced in many countries by metalaxyl-M, the fungicide enantiomerically enriched with the biologically active R-enantiomer. This "chiral switch" is expected to reduce the amount of pesticide released into the environment as well as potential side-effects on nontarget organisms. Detailed knowledge of the environmental behavior of such chiral compounds should include information on the chiral stability (interconversion of enantiomers). In the present study, the degradation/ dissipation of metalaxyl and its primary carboxylic acid metabolite (MX-acid) in soil was investigated under laboratory conditions using enantioselective gas chromatography mass spectrometry (GC-MS). Racemic and the enantiopure R- and S-compounds were incubated in separate experiments. The degradation of metalaxyl was shown to be enantioselective with the fungicidally active R-enantiomer being faster degraded than the inactive S-enantiomer, resulting in residues enriched with S-metalaxyl when the racemic compound was incubated. The relatively high enantioselectivity suggests that degradation/dissipation was largely biological. The data indicated a conversion of 40-50% of metalaxyl to MX-acid, and the remaining metalaxyl being degraded via other pathways. The degradation of MX-acid was also enantioselective. Metalaxyl and MX-acid were both configurationally stable in soil, showing no interconversion of R- to S-enantiomers, and vice-versa. Furthermore, the conversion of metalaxyl to MX-acid proceeded with retention of configuration. Degradation followed approximate first-order kinetics but showed significant lag phases.     

Combined sewer overflows to surface waters detected by the anthropogenic marker caffeine

Continuous progress in wastewater treatment technology and the growing number of households connected to wastewater treatment plants (WWTPs) have generally resulted in decreased environmental loading of many pollutants. Nonetheless, further reduction of pollutant inputs is required to improve the quality of surface waters in densely populated areas. In this context, the relative contribution of combined sewer overflows as sources of wastewater-derived contaminants has attracted more and more attention, but the quantitative importance of these overflows has barely been investigated. In this study, caffeine was successfully used as a chemical marker to estimate the fraction of sewer overflows in the catchment area of lake Greifensee, Switzerland. Caffeine is a ubiquitous compound in raw, domestic wastewater with typical per capita loads of approximately 16 mg person(-1) d(-1). In WWTPs of the Greifensee region, caffeine is largely eliminated (>99%), resulting in much smaller loads of < or = 0.15 mg person(-1) d(-1) in treated wastewater. However, in receiving streams as in the inflows to Greifensee, caffeine loads (0.1-1.6 mg person(-1) d(-1)) were higher than those in WWTP effluents, indicating additional sources. As the loads in the streams correlated with precipitation during sampling, it was concluded that combined sewer overflows were the most likely source of caffeine. Using a mass balance approach, it was possible to determine the fraction of wastewater (in dry weather equivalents) discharged untreated to the receiving streams (up to 10%, annual mean, approximately 2-3%). The concept of caffeine as a marker for combined sewer overflows was then applied to estimate phosphorus inputs to Greifensee with untreated and treated wastewater (approximately 1.5 and 2.0 t P y(-1), respectively), which corresponded well with P inputs determined in a separate study based on hydraulic considerations. For compounds with high elimination in WWTPs such as phosphorus (96-98% in the Greifensee area), inputs from combined sewer overflows are thus of similar magnitude as inputs from treated wastewater. The study demonstrated that caffeine is a suitable marker for untreated wastewater (from combined sewer overflows, direct discharges, etc.), but its sensitivity depends on regional conditions and decreases with decreasing elimination efficiency in WWTPs.     

Preexposure to a nonaggressive opponent prevents low-intensity, social conflict analgesia in mice.

In a first experiment, exposure of DBA/2 mice to a small number of attack bites by a C57BL/6 mouse resulted in a low-intensity analgesia as assessed by the tail-flick test. The analgesia dissipated within 10 min and was insensitive to naloxone (10 mg/kg, sc) but was antagonized by the irreversible opioid antagonist beta-chlornaltrexamine (5 mg/kg, sc). In a second experiment, preexposure to a nonaggressive C57BL/6 opponent prevented low-intensity analgesia induced by a small number of attack bites 24 hr later. The preexposure effect was abolished by naloxone (10 mg/kg, sc) given before the nonaggressive confrontation. This suggests that the release of endogenous opioids during preexposure interferes with the subsequent activation of endogenous opioid-mediated pain control mechanisms. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

肾上腺髓质素逆转去甲肾上腺素和内皮素的缩血管作用

目的 肾上腺髓质素(ADM) 为新型的血管扩张物质,有关 ADM与其它血管收缩物质的相互作用尚无报道。方法 本文以 14 例正常志愿者为对象,分两组经肱动脉分别注射 ADM或/和去甲肾上腺素(NE) (n =7),及 ADM或/和内皮素(n =7),观察前臂血流量的变化,并将单独用药和联合用药进行比较 。结果 经肱动脉注射 ADM,可使前臂血流量较用药前增加 3倍,血管扩张作用在停药后 40 min 逐渐消失。经肱动脉注射 NE 或内皮素,分别使前臂血流量下降 61%和73%。低浓度的 ADM与 NE 或内皮素联合输注,即可完全逆转后两者的血管收缩作用。结论 ADM为强烈的血管扩张剂,单次注射作用持续约 40 min 。在前臂阻力血管低浓度的 ADM可以逆转高浓度的 NE 或内皮素的血管收缩作用 。     

A study on the causes for the elevated n−3 fatty acids in cows' milk of alpine origin

The influence of grass-only diets either from rye-grass-dominated lowland pastures (400 m above sea level) or botanically diverse alpine pastures (2000 m) on the FA profile of milk was investigated using three groups of six Brown Swiss cows each. Two groups were fed grass-only on pasture (P) or freshly harvested in barn (B), both for two experimental periods in the lowlands and, consecutively, two periods on the alp. Group C served as the control, receiving a silage-concentrate diet and permanently staying in the lowlands. Effects of vegetation stage or pasture vs. barn feeding on milk fat composition were negligible. Compared with the control, α-linoleic acid (18∶3n−3) consumption was elevated in groups P and B (79%, P<0.001) during the lowland periods but decreased on the alp to the level of C owing to feed intake depression and lower 18∶3n−3 concentration in the alpine forage. Average 18∶3n−3 contents of milk fat were higher in groups, P and B than in C by 33% (P<0.01) at low and by 96% (P<0.001) at high altitude, indicating that 18∶3n−3 levels in milk were to some extent independent of 18∶3n−3 consumption. The cis-9,trans-11 CLA content in milk of grass-fed cows was higher compared with C but lower for the alpine vs. lowland periods whereas the trans-11, cis-13 isomer further increased with altitude. Long-chain n−3 FA and phytanic acid increased while arachidonic acid decreased with grass-only feeding, but none of them responded to altitude. Grass-only feeding increased milk α-tocopherol concentration by 86 and 134% at low and high altitude (P<0.001), respectively. Changes in the ruminal ecosystem due to energy shortage or specific secondary plant metabolites are discussed as possible causes for the high 18∶3n−3 concentrations in alpine milk.     

PROBABLE GAS HYDRATE IN CONTINENTAL SLOPE EAST OF THE NORTH ISLAND, NEW ZEALAND

Anomolous seismic horizons which (1) are strongly reflective, i.e. have a high impedence contrast; (2)cut across bedding planes of sediments;(3)are subparallel with the sea floor; and (4)increase their sub-bottom depth with increasing depth of sea floor (and thus with decreasing temperature of bottom water) are tentavely identifed as the base of a gas hydrate layer. The anamalous reflections occur below waters 1000-2500m deep, and along 500km of the continental slope. Some 10–20,000 sq km appear to be underlain by gas hydrates.
The hydrate layer is often associated with structural anomalies(anticlines, tilted faultblocks). These would allow gas to migrate up-dip into pressure and temperature conditions suitable for hydrate formation. Since the hydrate-cemented layer itself acts as a barrier to gas migration, free gas will be trapped and accumulated in the sediments beneath it.
It is concluded that huge amounts of hydrocarbon gas, both free gas and solid hydrate, have accumulated in this continental margin. On land, gas and oil generation is widespread, mainly originating from overpressured, Lower Teritiary to Upper Cretaceous shales. From seismic evidence the same formations appear to extend under the shelf and continental slope. The extensive occurence of gas hydrates would confirm that organicrich, terrigenous sediments have extensively been deposited in these areas.     

Stable hydrogen and oxygen isotope composition of waters from mine tailings in different climatic environments

The stable isotope composition of waters (delta2H, delta18O) can be used as a natural tracer of hydrologic processes in systems affected by acid mine drainage. We investigated the delta2H and delta18O values of pore waters from four oxidizing sulfidic mine tailings impoundments in different climatic regions of Chile (Piuquenes at La Andina with Alpine climate, Cauquenes and Carén at El Teniente with Mediterranean climate, and Talabre at the Chuquicamata deposit with hyperarid climate). No clear relationship was found between altitude and isotopic composition. The observed displacement of the tailings pore waters from the local meteoric water line toward higher delta18O values (by approximately +2 per thousand delta18O relative to delta2H) is partly due to water-rock interaction processes, including hydration and O-isotope exchange with sulfates and Fe(III) oxyhydroxides produced by pyrite oxidation. In most tailings, from the saturated zone toward the surface, isotopically different zones can be distinguished. Zone I is characterized by an upward depletion of 2H and 18O in the pore waters from the saturated zone and the lowermost vadose zone, due to ascending diffused isotopically light water triggered by the constant loss of water vapor by evaporation at the surface. In zone II, the capillary flow of a mix of vapor and liquid water causes an evaporative isotopic enrichment in 2H and 18O. At the top of the tailings in dry climate a zone III between the capillary zone and the surface contains isotopically light diffused and atmospheric water vapor. In temperate climates, the upper part of the profile is affected by recent rainfall and zone III may not differ isotopically from zone II.     

Protein composition, plasmin activity and cheesemaking properties of cows' milk produced at two altitudes from hay of lowland and high-alpine origins

The influence of high altitude, alpine origin of the forage and roughage-only diets on milk protein content and composition, plasmin activity and cheesemaking properties was investigated. There were four treatment groups, each consisting of six dairy cows in early to mid-lactation. Two groups were fed only with hay ad libitum either at 2000 m or at 400 m a.s.l. One group, kept in the lowlands, was pair-fed to the alpine-site group and another group received a mixed diet of silages, hay and concentrates. Two hay types, harvested either at the alpine site or in the lowlands, were offered to all cows fed with hay alone, following a change-over design in three periods each of 3 weeks. In the respective third week, milk was sampled at every milking. Hay of alpine origin significantly reduced milk protein, in particular whey proteins, which is why the casein number increased. kappa-Casein proportion in total casein was reduced and its glycosylation was increased by the alpine hay. The apparent plasminogen-derived activity was reduced when alpine hay was given, but apparent plasmin activity and rennet coagulation properties of the milk were not affected by hay type. Independent of hay type, the high altitude group showed a significantly reduced milk protein content, lower glycosylation of kappa-casein and impaired rennet coagulation properties. For several of the traits, the trend was the same in the pair-fed group. There was no effect of altitude on apparent plasmin activity. Hay-alone v. the mixed diet resulted initially in marked declines in milk protein content but did not impair cheesemaking properties. Thus the extensive diet without concentrates, typical of high-alpine conditions, contributed less to the overall effect of extensive alpine v. intensive lowland feeding systems than hay quality and altitude did. In conclusion, certain positive influences of the alpine sojourn of cows on cheese processing quality are overruled by the major adverse impact of lower milk protein content.