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。     

Upwelling and river runoff as sources of dissolved nitrous oxide to the Alsea estuary,Oregon

Surface waters of Alsea Bay, an unpolluted estuary on the Oregon coast, were analysed for nitrous oxide, nitrate and nitrite on a weekly or biweekly basis during the summer of 1979. The estuary was found to be a variable source of N₂O to the atmosphere. Large and rapid increases in the concentrations of N₂O, NO₃^?, and NO₂^? occurred at the beginning of the sampling period and are attributed to the influx of nutrient-rich upwelling water into the estuary with the tide. The subsequent decline in concentrations of nitrate, nitrite and nitrous oxide over the remainder of the summer is attributed to a decrease in upwelling intensity, a decline in nitrification rates and to assimilatory nitrate reduction. Measurements of nitrous oxide at six stations along the Alsea River were also made in September and October before and after the onset of the rainy season. Samples taken after flood conditions were established were systematically 50% higher than pre-flood samples. The data suggest that soil runoff results in elevated concentrations of N₂O in rivers.     

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.     

Nitrogen uptake,ammonium oxidation and nitrous oxide (N2O) levels in the coastal waters of western Cook Strait,New Zealand

Vertical measurements of $\text{NH}{}_4{}^{\mathrm{+}}$, $\text{NO}{}_3{}^{\mathrm{?}}$ and N₂O concentrations, $\text{NO}{}_3{}^{\mathrm{?}}$ and $\text{NH}{}_4{}^{\mathrm{+}}$ uptake, and $\text{NH}{}_4{}^{\mathrm{+}}$ oxidation rates were measured at 5 sites in western Cook Strait, New Zealand, between 31 March and 3 April 1983. Nitrate increased with depth at all stations reaching a maximum of 10.5 μg-atom $\text{NO}{}_3{}^{\mathrm{?}}\text{N l}{}^{\mathrm{?1}}$ at the most strongly stratified station whereas $\text{NH}{}_4{}^{\mathrm{+}}$ was relatively constant with depth at all stations (～0.1 μg-atom $\text{NH}{}_4{}^{\mathrm{+}}\text{N l}{}^{\mathrm{?1}}$). The highest rates of $\text{NH}{}_4{}^{\mathrm{+}}$ oxidation generally occurred in the near surface waters and decreased with depth. N₂O levels were near saturation with respect to the air above the sea surface and showed no obvious changes during 24 h incubation. $\text{NH}{}_4{}^{\mathrm{+}}$ oxidation by nitrifying bacteria may account for about 30% of the total $\text{NH}{}_4{}^{\mathrm{+}}$ utilization (i.e. bacterial+agal) and, assuming oxidation through to $\text{NO}{}_3{}^{\mathrm{?}}$, may supply about 40% of the algal requirements of $\text{NO}{}_3{}^{\mathrm{?}}$ in the study area. These results suggest that bacterial nitrification is of potential importance to the nitrogen dynamics of the western Cook Strait, particularly with respect to the nitrogen demands of the phytoplankton.     

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     

Seasonally Hypersaline Estuaries in Mediterranean-climate Regions

Data collected in three Californian estuaries indicate that hypersaline conditions exist during the dry summers typical of a Mediterranean climate. The generalised seasonal and longitudinal hydrographic structures are described and explained. It is argued that this seasonal hypersalinity is common and that it represents a major class of estuaries. The observed accumulation of salt indicates surprisingly long residence times in small basins which have free exchange with the ocean. This semi-isolation of the inner basin leads to a large build-up or severe depletion of nutrients, pollutants and plankton in these systems. Of concern are the trends to increase pollutant loading in the same systems that are experiencing an increase in residence times owing to freshwater extraction in the watershed.