Optimization of the Sampling Technique for the Determination of Dissolved Hydrogen in Groundwater

In this study a field‐sampling technique for dissolved hydrogen (H₂) in groundwater will be presented which allows the transport of gaseous samples into the laboratory for further analysis. The method consists of transferring the headspace trapped in a gas‐sampling bulb which is continuously purged by groundwater into previously evacuated vials using a gas‐tight syringe. Three transfer steps with preceding evacuation of the vial led to a H₂‐recovery of 100 % in laboratory experiments. The method has been applied to determine H₂ concentrations in an aquifer contaminated with chlorinated solvents. Tests concerning the effect of different pumping techniques on H₂ concentrations revealed that most reliable values were obtained with a bladder pump, while an electrically driven submersible pump generated considerable amounts of hydrogen due to electrochemical interactions with the sampled water. Concentrations of dissolved hydrogen in field and laboratory samples were about two orders of magnitude higher when sampling was performed with the electrically driven submersible pump compared to sampling with the bladder pump and a peristaltic pump. Lab experiments with a Plexiglas reservoir to produce H₂‐enriched water were used to study the effect of two tubing materials (PVC, polyamide) on H₂ losses. PVC tubing turned out to allow transfer of H₂‐enriched water over 25 m without significant losses, while PA‐tubing was not suitable for sampling of H₂.     

Water and sediment outbursts from advanced Franz Josef Glacier,New Zealand

The Franz Josef Glacier, Westland, New Zealand, has a history of catastrophic sediment‐laden outburst ?oods associated with extreme rainfall events when the glacier toe is advanced over its own sediments. Consideration of these events and inspection of recent sediment deposits suggest that there are three distinct modes of outburst. The ?rst is associated with fans fed by over?ow along the glacier margin. As the glacier has advanced across its own fore?eld gravels, it is inferred that the primary drainage conduit has developed a reach of negative slope. In high ?ows massive boulders can block the conduit, trapping lesser clasts. The resulting backup of water causes over?ows through marginal moulins, producing the fan type of deposit. The second type of outburst deposits massive imbricated boulders at a greater or lesser distance from the glacier portal. In this case, pressure buildup drives the blockage out of the portal where the boulders deposit. Smaller materials are generally carried away. The third type consists of very shallow ?ows, and produces massive gravel deposits of uncertain provenance. In this condition, the excess pressure in the conduit results in slight uplift of the glacier and widespread discharge of water and sediment below the glacier snout; gravels and smaller sediments are laid down in a massive deposit across the fore?eld. The massive, boulder‐veneered deposit from the December 1995 outburst is interpreted in the light of the above mechanisms as a hyperconcentrated ?ow deposit from hydraulic jacking, overlain by boulders emplaced by a subsequent conduit outburst. A possible association of outbursts with the present advanced position of the glacier is suggested. Copyright © 2003 John Wiley & Sons, Ltd.     

Paleoecology of two marine oxygen isotope stage 7 sites correlated by the Sheep Creek tephra, northwestern North America

Pollen analysis at two sites, correlated by the presence of the 190,000 yr-old Sheep Creek tephra, documents fluctuations in vegetation and climate consistent with this date and indicates that the records span marine oxygen isotope stage 7 and the stage 6/7 transition. Dawson Cut, near Fairbanks, Alaska, provides a 5.2-m-long pollen record of interglacial boreal forest succeeded by shrub tundra and then forest/tundra. Ash Bend, Stewart River, central Yukon, provides a 9.5-m-long record of interglacial boreal forest succeeded by forest/tundra, shrub tundra, and herbaceous tundra. The replacement of forest at both sites by more open or tundra vegetation indicates warm interglacial conditions giving way to cold and arid climate. It is not clear whether stage 7 was warmer than the present. The warm-cool-warm climate oscillation evident at both sites may correlate to Lake Baikal substages 7a, 7b, and 7c. Sheep Creek tephra fell on forest/tundra vegetation.     

6-硝基-2-苯并噻唑重氮氨基偶氮苯与铜的显色反应及其应用

在pH10～12的Na2B4O7-NaOH缓冲溶液中,TritonX-100表面活性剂存在下,6-硝基-2-苯并噻唑重氮氨基偶氮苯与铜发生显色反应,生成2∶1的深红色配合物。配合物的最大吸收峰位于535nm处,表观摩尔吸光系数1.42×105L·mol-1·cm-1。Cu2+的浓度在0～400μg/L符合比尔定律。用拟定方法测定铝合金及铜矿石样品中的微量铜,结果与原子吸收法结果相符,6次测定的RSD<3%。     

建筑物沉降规律的综合时序分析

建筑物的沉降监测数据序列具有趋势变化和随机变化的特点，本文针对两种变化项的特点分别建立相应的数学模型，再将其组合起来建立综合数学模型，从总体上把握沉降数据序列的变化规律。实例计算分析表明，此方法具有较高的拟合精度和预测能力，具有一定的应用参考价值。     

Compositional variations (major and trace elements) of clinopyroxene and Ti-andradite from pyroxenite, ijolite and nepheline syenite, Alnö Island, Sweden

Clinopyroxenes from pyroxenite, ijolite and nepheline syenite from the main intrusion of the Alnö complex define two sub-parallel compositional trends with respect to Na, Ca and Fe_TOT plotted against alkali-pyroxene fractionation index (Na–Mg). Both trends define a smooth fractionation of increasing Na and Fe_TOT and decreasing Ca with increasing Na–Mg, but one set of samples contain clinopyroxenes that constantly plot at higher Na and lower Fe_TOT and Ca (at similar Na–Mg) than the rest of the samples. Clinopyroxenes with higher Ca and Fe_TOT and lower Na (trend 1) co-exist with substantial amounts of Ti-andradite (up to 70 vol.%), while the sample set defining the more Na-rich trend (trend 2) lack co-existing Ti-andradite. Clinopyroxenes from both trends show fractionated REE patterns with a distinct difference in HREE content, reflecting the content of co-existing Ti-andradite. The rocks of the first Ti-andradite-bearing trend crystallized slightly prior to the rocks of the second trend, probably from a primitive, Ca- and Ti-rich nephelinitic magma. Crystallisation of pyroxenite and melteigite occurred under low aSiO₂ and high aCaO and aTiO₂ as evidenced by the presence of perovskite and sometimes substantial amounts of magnetite. Subsequent increase in aSiO₂ is evidenced in the overgrowth of perovskite by titanite, which in turn is overgrown by Ti-andradite. Nepheline syenitic residuals crystallized under higher aSiO₂ and aNa₂O and lower aCaO and aTiO₂, which reduced Ti-andradite into an accessory phase and produced more Si- and Na-rich clinopyroxenes. Some of these residuals probably also mixed with new primitive magma producing a hybrid magma that crystallised the more Na-rich and Ca- and Fe_TOT-poor clinopyroxenes of trend 2. The complete lack of Ti-andradite in these rocks indicates different crystallisation conditions and also a different magma composition.     

Vegetation history of the penultimate glacial period (Marine isotope stage 6) at Ioannina,north‐west Greece

The vegetational history of the penultimate glacial period, Marine Isotope Stage (MIS) 6 (c. 185–135 ka), has remained relatively unexplored. Here we present a new record from the Ioannina basin, north‐west Greece, which constitutes the highest‐resolution terrestrial pollen record for this interval produced to date. It shows that the vegetation history of MIS 6 in this region can be divided into two parts: an early period (185–155 ka) with pronounced oscillations in tree population extent, and a later period (155–135 ka) with much smaller tree populations and subdued oscillations. This pattern is analogous to the MIS 3/MIS 2 division during the last glacial in the same sequence, although the early part of MIS 6 had larger Pinus populations and fewer temperate trees relative to the equivalent interval in MIS 3. This implies cooler and wetter conditions, which is somewhat counterintuitive given the high summer insolation during MIS 6e, but is in line with other palaeoclimatic evidence from the Mediterranean. Comparison with North Atlantic records suggests that despite the absence of pronounced iceberg discharges during MIS 6, North Atlantic millennial‐scale variability had a significant downstream impact on tree populations in north‐west Greece. Copyright © 2011 John Wiley & Sons, Ltd.     

Iron isotopic systematics of UHP eclogites respond to oxidizing fluid during exhumation

The iron stable isotope compositions (δ⁵⁶Fe) and iron valence states of ultrahigh‐pressure eclogites from Bixiling in the Dabie orogen belt, China, were measured to trace the changes of geochemical conditions during vertical transportation of earth materials, for example, oxygen fugacity. The bulk Fe³⁺/ΣFe ratios of retrograde eclogites, determined by Mössbauer spectroscopy, are consistently higher than those of fresh eclogites, suggesting oxidation during retrograde metamorphism and fluid infiltration. The studied eclogites (five samples) display limited mid‐ocean ridge basalts (MORB)‐like (~0.10‰) δ⁵⁶Fe values, which are indistinguishable from their protoliths, that is, gabbro cumulates formed through differentiation of mantle‐derived basaltic magma. This suggests that Fe isotope fractionation during continental subduction is limited. Garnet separates display limited δ⁵⁶Fe variation ranging from ?0.08 ± 0.07 ‰ to 0.02 ± 0.07‰, whereas coexisting omphacite displays a large variation of δ⁵⁶Fe values from 0.15 ± 0.07‰ to 0.47 ± 0.07‰. Omphacite also has highly variable Fe³⁺/ΣFe ratios from 0.367 ± 0.025 to 0.598 ± 0.024, indicating modification after peak metamorphism. Omphacite from retrograde eclogites has elevated Fe³⁺/ΣFe ratios (0.54–0.60) compared to that from fresh eclogites (~0.37), whereas garnet displays a narrow range of ferric iron content with Fe³⁺/ΣFe ratios from 0.039 ± 0.013 to 0.065 ± 0.022. The homogenous δ⁵⁶Fe values and Fe³⁺/ΣFe ratios of garnet suggest that it survived the retrograde metamorphism and preserved its Fe‐isotopic features and ferric contents of peak metamorphism. Because of similar diffusion rates of Fe and Mg in garnet and omphacite, and constant Δ²⁶Mg_{omphacite‐garnet} values (1.14 ± 0.04‰), equilibrium iron isotope fractionation between garnet and omphacite was probably achieved during peak metamorphism. Elevated Fe³⁺/ΣFe ratios of omphacite from retrograde eclogites and variant Δ⁵⁶Fe_{omphacite‐garnet} values of the studied eclogites (0.13 ± 0.10‰ to 0.48 ± 0.10‰) indicate that oxidized geofluid infiltration resulted in the elevation of δ⁵⁶Fe values of omphacite during retrograde metamorphism.