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.     

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.     

Possible chemical structures and biological precursors of different vitrinites in coal measure in Northwest China

Chemical structure of Jurassic vitrinites isolated from the coals in basins in NW China have been checked using solid state ¹³C NMR and flash pyrolysis-GC/MS. Study shows some Jurassic collodetrinites are rich in aliphatic products in pyrolysates, consisting with the high amount of methylene carbon in ¹³C NMR spectra. In contrast, pyrolysates of Jurassic collotelinites are rich in phenols and alkylbenzenes. Also one Pennsylvanian and one Permian vitrinite selected from the Ordos basin, NW China have been checked for comparison. The proportion of aliphatics is low in pyrolysates, and aliphatic carbon peak in ¹³C NMR spectrum of Permian vitrinite is mostly composed of gas-prone carbons compared with collodetrinites in those Jurassic basins. But both pyrolysis and ¹³C NMR data shows the Pennsylvanian vitrinite is not only gas-prone but also oil-prone. Relatively high proportion of long chain aliphatic structure of some Jurassic vitrinite in Junggar, Turpan-Hami basins may be due to the contribution of liptodetrinites, which may be included during the formation of vitrinites. And it seems that suberinite is the most possible precursor of long chain aliphatics in the structure of Jurassic collodetrinite.     

Oxygen Isotope Evidence for Chemical Interaction of Ki lauea Historical Magmas with Basement Rocks

Klauea historical summit lavas have a wide range in matrix ¹⁸O_VSMOWvalues (4·9–5·6) with lower values in rockserupted following a major summit collapse or eruptive hiatus.In contrast, ¹⁸O values for olivines in most of these lavasare nearly constant (5·1 ± 0·1). The disequilibriumbetween matrix and olivine ¹⁸O values in many samples indicatesthat the lower matrix values were acquired by the magma afterolivine growth, probably just before or during eruption. BothMauna Loa and Klauea basement rocks are the likely sources ofthe contamination, based on O, Pb and Sr isotope data. However,the extent of crustal contamination of Klauea historical magmasis probably minor (< 12%, depending on the assumed contaminant)and it is superimposed on a longer-term, cyclic geochemicalvariation that reflects source heterogeneity. Klauea's heterogeneoussource, which is well represented by the historical summit lavas,probably has magma ¹⁸O values within the normal mid-ocean ridgebasalt mantle range (5·4–5·8) based on thenew olivine ¹⁸O values. KEY WORDS: Hawaii; Klauea; basalt; oxygen isotopes; crustal contamination     

Gravity torques for surface waves

The effects of the gravity torques acting on the angular momentum of surface gravity waves are calculated theoretically. For short crested waves the gravity torque is caused by the force of gravity on the orbiting fluid particles acting down the slopes of the crests and troughs and in the direction parallel to the crests and troughs. The gravity torque tries to rotate the angular momentum vectors, and thus the waves themselves, counterclockwise in the horizontal plane, as viewed from above, in both hemispheres. The amount of rotation per unit time is computed to be significant assuming reasonable values for the along-crest and trough slopes for waves in a storm area. The gravity torque has a frequency which is double the frequency of the waves. For long crested waves the gravity torque acts in the vertical plane of the orbit and tries to decelerate the particles when they rise and accelerate them when they fall. By disrupting the horizontal cyclostrophic balance of forces on the fluid particles (centrifugal force versus pressure force) the gravity torque accounts qualitatively for the three characteristics of breaking waves: that they break at the surface, that they break at the crest, and that the crest breaks in the direction of wave propagation.     

分离入射波与反射波的解析方法

提出了一种新的分离入射波和反射波的解析方法（AM）。利用两点处的 波高信息，运用Hilbert变换得到波浪信号在复域内的解析表达式，不需要计算合成波高和相位差即可实现信号的分离。根据分离结果，可以精确地估计入射波与反射波的幅值以及反射系数等参数，能够获得入射波与反射波之间的相位信息，并且可方便地用于不规则波的分离。文中通过数值模拟与物理模型实验对AM法进行了检验，所得的结果与实际值非常吻合。     

Observations of the Labrador Sea eddy field

This paper is an observational study of small-scale coherent eddies in the Labrador Sea, a region of dense water formation thought to be of considerable importance to the North Atlantic overturning circulation. Numerical studies of deep convection emphasize coherent eddies as a mechanism for the lateral transport of heat, yet their small size has hindered observational progress. A large part of this paper is therefore devoted to developing new methods for identifying and describing coherent eddies in two observational platforms, current meter moorings and satellite altimetry. Details of the current and water mass structure of individual eddy events, as they are swept past by an advecting flow, can then be extracted from the mooring data. A transition is seen during mid-1997, with long-lived boundary current eddies dominating the central Labrador Sea year-round after this time, and convectively formed eddies similar to those seen in deep convection modeling studies apparent prior to this time. The TOPEX / Poseidon altimeter covers the Labrador Sea with a loose “net” of observations, through which coherent eddies can seem to appear and disappear. By concentrating on locating and describing anomalous events in individual altimeter tracks, a portrait of the spatial and temporal variability of the underlying eddy field can be constructed. The altimeter results reveal an annual “pulsation” of energy and of coherent eddies originating during the late fall at a particular location in the boundary current, pinpointing the time and place of the boundary current-type eddy formation. The interannual variability seen at the mooring is reproduced, but the mooring site is found to be within a localized region of greatly enhanced eddy activity. Notably lacking in both the annual cycle and interannual variability is a clear relationship between the eddies or eddy energy and the intensity of wintertime cooling. These eddy observations, as well as hydrographic evidence, suggest an active role for boundary current dynamics in shaping the energetics and water mass properties of the interior region.