量子化学方法研究氯代苯酚类化合物对水生物毒性的构效关系

对20个氯代苯酚类化合物进行了CNDO/2量子化学计算,讨论了化合物电子结构与其对水生物翻车鱼(Bluegill)、花鳉鱼(Guppy)、和虾(Shrimp)半致死量之间的关系,分别获得了表示其构效关系的三个线性方程,它们的显著性均远高于α=0.01水平。结果表明:氯代苯酚化合物苯环上碳原子的兀电荷之和(∑Qπ_R)越大苯环上碳原子的净电荷之和(∑Q_R)越大,或LUMO轨道能(E_(LUMO))越低,均使化合物对Bluegill和Guppy水生物的毒性增大;而化合物苯环上羟基邻位的碳原子的兀电荷布居(P_3)越大,同时HOMO轨道能E_(HOMO)越高,则化合物对Shrimp毒性也越大。据此,可预测氯代苯酚类化合物对上述三种水生物的毒性。     

40Ar/39Ar and oxygen isotope studies of polymetamorphism from Tinos Island, Cycladic blueschist belt, Greece

Abstract Petrological, oxygen isotope and ⁴⁰Ar/³⁹Ar studies were used to constrain the Tertiary metamorphic evolution of the lower tectonic unit of the Cyclades on Tinos. Polyphase high-pressure metamorphism reached pressures in excess of 15 kbar, based on measurements of the Si content in potassic white mica. Temperatures of 450–500° C at the thermal peak of high-pressure metamorphism were estimated from critical metamorphic assemblages, the validity of which is confirmed by a quartz–magnetite oxygen isotope temperature of 470° C. Some ⁴⁰Ar/³⁹Ar spectra of white mica give plateau ages of 44–40 Ma that are considered to represent dynamic recrystallization under peak or slightly post-peak high-pressure metamorphic conditions. Early stages in the prograde high-pressure evolution may be documented by older apparent ages in the high-temperature steps of some spectra. Eclogite to epidote blueschist facies mineralogies were partially or totally replaced by retrograde greenschist facies assemblages during exhumation. Oxygen isotope thermometry of four quartz–magnetite pairs from greenschist samples gives temperatures of 440–470° C which cannot be distinguished from those deduced for the high-pressure event. The exhumation and overprint is documented by decreasing ages of 32–28 Ma in some greenschists and late-stage blueschist rocks, and ages of 30–20 Ma in the lower temperature steps of the Ar release patterns of blueschist micas. Almost flat parts of Ar–Ar release spectra of some greenschist micas gave ages of 23–21 Ma which are assumed to represent incomplete resetting caused by a renewed prograde phase of greenschist metamorphism. Oxygen isotope compositions of blueschist and greenschist facies minerals show no evidence for the infiltration of a δ¹⁸O-enriched fluid. Rather, the compositions indicate that fluid to rock ratios were very low, the isotopic compositions being primarily controlled by those of the protolith rocks. We assume that the fundamental control catalysing the transformation of blueschists into greenschists and the associated resetting of their isotopic systems was the selective infiltration of metamorphic fluid. A quartz–magnetite sample from a contact metamorphic skarn, taken near the Miocene monzogranite of Tinos, gave an oxygen isotope temperature of 555° C and calculated water composition of 9.1%. The value of δ¹⁸O obtained from this water is consistent with a primary magmatic fluid, but is lower than that of fluids associated with the greenschist overprint, which indicates that the latter event cannot be directly related to the monozogranite intrusion.     

A dated cave sediment record of Pleistocene transgressions on Berry Head,Southwest England

Berry Head, a limestone headland in Torbay, southwest England, exhibits a series of subaerial marine erosion platforms and raised beaches spanning an altitude range of 97 m. Solution caves on the headland show preferred horizontal development at elevations that are correlated with the marine erosion platforms, and developed in a marine/freshwater mixing zone whose position was controlled by high sea-level still-stands. Corbridge Cave in Berry Head Quarry lies below the raised beaches in Torbay, and contains evidence of three marine transgressions in the form of fine-grained marine ponding deposits with a marine microfauna. Uranium-series dating of intercalated speleothems indicates that a transgression during oxygen isotope stage 5e reached an elevation of 5.8 m OD, while an earlier transgression (probably during stage 7) reached at least 7.2 m OD. These findings are used to constrain possible interpretations of the aminostratigraphy of raised beaches in Southwest Britain, and a correlation of the Unnamed Stage of Bowen, Sykes, Reeves, Miller, Andrews, Brew and Hare with oxygen isotope stage 5e is proposed.     

Exposure dating and reinterpretation of coarse debris accumulations (‘rock glaciers’) in the Cairngorm Mountains,Scotland

Relict rock glaciers have considerable potential for contributing to palaeoclimatic reconstruction, but this potential is often undermined by lack of dating control and problems of interpretation. Here we reinvestigate and date four proposed ‘rock glaciers’ in the Cairngorm Mountains and show that the morphology of only one of these appears consistent with that of a true rock glacier produced by creep of underlying ice or ice‐rich sediment. All four features comprise rockslide or rock avalanche runout debris, and the possibility that all four represent unmodified runout accumulations cannot be discounted. Surface exposure dating of the four debris accumulations using cosmogenic ¹⁰Be produced uncertainty‐weighted mean ages of 15.4 ± 0.8 ka, 16.2 ± 1.0 ka, 12.1 ± 0.6 ka and 12.7 ± 0.8 ka. All four ages imply emplacement under cold stadial conditions, two prior to the Windermere Interstade of ca. 14.5–12.9 cal. ka BP and two during the Loch Lomond Stade of ca. 12.9–11.5 cal. ka BP. The above ages indicate that paraglacial rock‐slope failure on granite rockwalls occurred within a few millennia after deglaciation. The mean exposure ages obtained for runout debris at two sites – Strath Nethy (16.2 ± 1.0 ka) and Lairig Ghru (15.4 ± 0.8 ka) – are consistent with basal radiocarbon ages from Loch Etteridge, 22 km to the southwest (mean = 15.6 ± 0.3 cal. ka BP) and imply widespread deglaciation of the Cairngorms and adjacent valleys before 15 ka and possibly 16 ka. Copyright © 2008 John Wiley & Sons, Ltd.     

Luminescence dating of sand–loess sequences and response of Mu Us and Otindag sand fields (north China) to climatic changes

The sand–loess transition zone in north China is sensitive to climate change, and is an ideal place to investigate past environmental changes. However, past climate change at millennial–centennial timescales in this region has not been well reconstructed because of limited numerical dating. Alternations of sandy loam soils with aeolian sand layers in the Mu Us and Otindag sand fields, which lie along the sand–loess transition zone, indicate multiple intervals of dune activity and stability. This change is probably a response to variations of the East Asian monsoon climate during the late Quaternary. The single aliquot regeneration (SAR) optically stimulated luminescence (OSL) dating protocol, which has been successfully applied to aeolian deposits worldwide, is applied to these two sand fields in this study. The OSL ages provide reliable constraints for reconstruction of past climate changes at suborbital timescale. Sections in both sand fields contain aeolian sand beds recording millennial‐scale episodes of dry climate and widespread dune activation, including episodes at about the same time as Heinrich Event 5 and the Younger Dryas in the North Atlantic region. These results demonstrate the potential of aeolian sediments in semi‐arid north China to record millennial‐scale climatic events, and also suggest that dry–wet climate variation at the desert margin in China may be linked to climatic change elsewhere in the Northern Hemisphere, through atmospheric circulation. This article was published online on 27 November 2008. An error was subsequently identified. This notice is included in the online and print versions to indicate that both have been corrected (16 December 2008). Copyright © 2008 John Wiley & Sons, Ltd.     

Pan-African eclogite facies metamorphism of ultramafic rocks in the Shackleton Range, Antarctica

In the Shackleton Range of East Antarctica, garnet-bearing ultramafic rocks occur as lenses in supracrustal high-grade gneisses. In the presence of olivine, garnet is an unmistakable indicator of eclogite facies metamorphic conditions. The eclogite facies assemblages are only present in ultramafic rocks, particularly in pyroxenites, whereas other lithologies – including metabasites – lack such assemblages. We conclude that under high-temperature conditions, pyroxenites preserve high-pressure assemblages better than isofacial metabasites, provided the pressure is high enough to stabilize garnet–olivine assemblages (i.e. ≥18–20 kbar). The Shackleton Range ultramafic rocks experienced a clockwise P–T path and peak conditions of 800–850 °C and 23–25 kbar. These conditions correspond to ∼70 km depth of burial and a metamorphic gradient of 11–12 °C km⁻¹ that is typical of a convergent plate-margin setting. The age of metamorphism is defined by two garnet–whole-rock Sm–Nd isochrons that give ages of 525 ± 5 and 520 ± 14 Ma corresponding to the time of the Pan-African orogeny. These results are evidence of a Pan-African suture zone within the northern Shackleton Range. This suture marks the site of a palaeo-subduction zone that likely continues to the Herbert Mountains, where ophiolitic rocks of Neoproterozoic age testify to an ocean basin that was closed during Pan-African collision. The garnet-bearing ultramafic rocks in the Shackleton Range are the first known example of eclogite facies metamorphism in Antarctica that is related to the collision of East and West Gondwana and the first example of Pan-African eclogite facies ultramafic rocks worldwide. Eclogites in the Lanterman Range of the Transantarctic Mountains formed during subduction of the palaeo-Pacific beneath the East Antarctic craton.     

Short-term Climate Characteristics at Ny-(A)lesund over the Arctic Tundra Area

Based on the Germany Koldwey Station's 1994-2003 conventional observation hourly data, this paper conducts a statistical analysis on the short-term climate characteristics for an arctic tundra region (Ny-(A)lesund island) where our first arctic expedition station (Huanghe Station) was located. Affected by the North Atlantic warming current, this area has a humid temperate climate, and the air temperature at Ny-(A)lesund rose above 0 ℃ even during deep winter season during our research period. The wind speed in this area was low and appeared most at southeast direction. We find that the temperature at Ny-(A)lesund rose in the faster rate (0.68 ℃/10 a) than those at the whole Arctic area. Compared with the floating ices where our expedition conducted in the Arctic, Ny-(A)lesund was warmer and more humid and had lower wind speed. Comparison of the near surface air temperature derived by NCEP/NCAR reanalysis to the conventional measurements conducted at the Koldwey site in Ny-(A)lesund area shows a good agreement for winter season and a significant difference for summer season.     

Isobaric cooling and anti-clockwise P–T paths in the Variscan Odenwald Crystalline Complex, Germany

Mineral assemblages in Al₂O₃‐rich, SiO₂‐ and K₂O‐poor metapelitic rocks from the western Odenwald Crystalline Complex (Variscan Mid‐German Crystalline Rise, southern Germany) include corundum, spinel, cordierite, sillimanite, garnet and staurolite. Quartz is absent from almost all samples. Therefore, the applicability of conventional geothermobarometry is very limited or even impossible. Detailed petrographic investigation on selected samples permits inference of the sequence of appearance and disappearance of several mineral assemblages. The recognition of such partial re‐equilibration stages and their associated mineral assemblages, together with mineral stabilities predicted from KFMASH pseudosections, enables the determination of the pressure‐temperature (P–T) trajectories experienced by these rocks during the Variscan metamorphism. The rocks were metamorphosed under low‐P/high‐T conditions and underwent an anti‐clockwise P–T evolution. A pressure increase from about 2 kbar to 4 ± 0.5 kbar was accompanied by heating. Peak metamorphic conditions were reached at pressures of 4 ± 0.5 kbar and temperatures of at least 640 °C, probably even higher. The retrograde evolution is characterised by near‐isobaric cooling from ≥ 640 °C to approximately 550 °C. The rocks underwent the anti‐clockwise evolution in a subduction‐related magmatic arc setting. The close spatial association of the low‐P/high‐T rocks with recently discovered metabasic eclogites in the eastern part of the Odenwald Crystalline Complex may indicate a fossil paired metamorphic belt in the Central European Variscides.     

Fast iterative solution of large undrained soil‐structure interaction problems

In view of rapid developments in iterative solvers, it is timely to re‐examine the merits of using mixed formulation for incompressible problems. This paper presents extensive numerical studies to compare the accuracy of undrained solutions resulting from the standard displacement formulation with a penalty term and the two‐field mixed formulation. The standard displacement and two‐field mixed formulations are solved using both direct and iterative approaches to assess if it is cost‐effective to achieve more accurate solutions. Numerical studies of a simple footing problem show that the mixed formulation is able to solve the incompressible problem ‘exactly’, does not create pressure and stress instabilities, and obviate the need for an ad hoc penalty number. In addition, for large‐scale problems where it is not possible to perform direct solutions entirely within available random access memory, it turns out that the larger system of equations from mixed formulation also can be solved much more efficiently than the smaller system of equations arising from standard formulation by using the symmetric quasi‐minimal residual (SQMR) method with the generalized Jacobi (GJ) preconditioner. Iterative solution by SQMR with GJ preconditioning also is more elegant, faster, and more accurate than the popular Uzawa method. Copyright © 2003 John Wiley & Sons, Ltd.     

A 20‐ka climate record from Central Himalayan loess deposits

The southwest monsoon that dominated Central Himalaya has preserved loessic silt deposits preserved in patches that are proximal to periglacial areas. The occurrence of such silts suggests contemporary prevalence of cold and dry northwesterly winds. Field stratigraphy, geochemistry, mineral magnetism, infrared stimulated luminescence (IRSL) and radiocarbon dating has enabled reconstruction of an event chronology during the past 20 ka. Three events of loess accretion could be identified. The first two events of loess deposition occurred betweem 20 and 9 ka and were separated by a phase of moderate weathering. Pedogenesis at the end of this event gave rise to a well‐developed soil that was bracketed around 9 to > 4 ka. This was followed by the third phase of loess accretion that occurred around 4 to > 1 ka. Episodes of loess deposition and soil formation are interpreted in terms of changes in the strength of the Indian southwest monsoon. Copyright © 2005 John Wiley & Sons, Ltd.