开链冠醚2，6-二(8''''-喹啉氧甲基)-4-甲基-苯甲醚及其Ag( Ⅰ )、Cu( Ⅱ )、Ni( Ⅱ )配合物的合成与性质研究

设计合成一种尚未见文献报道的酚醚型双臂开链冠醚化合物L(L=2,6-二(8’-喹啉氧甲基)-4-甲基-苯甲醚)，经元素分析、IR、1HNMR、MS等方法确定了其组成和结构。其Ag(Ⅰ)、Cu(Ⅱ)、Ni(Ⅱ)固体配合物的元素分析结果表明金属离子不同，则其配合物的配位比(M∶L)不同，Ag(Ⅰ)配合物为1∶1，Cu(Ⅱ)、Ni(Ⅱ)配合物为2∶3。并运用热重-差热分析对其热稳定性进行初步研究。     

Se(IV)对藻蓝蛋白分子的氧化及纳米Se(0)的生成

从钝顶螺旋藻(Spirulina platensis)中提取纯化藻蓝蛋白(Phycocyanin,PC),光吸收值A620/A280为3.1,观察Se(Ⅳ)与PC相互作用的光谱行为及红硒化现象。光谱检测发现,加入SeO32-后,PC在620 nm的特征光吸收减弱,并随Se(Ⅳ)浓度增加和时间延长单调降低,278 nm和347 nm的光吸收增强;PC的荧光发射和荧光激发也均呈现衰减。另外,PC与Na2SeO3相互作用后,观察到红硒化现象,透射电镜(TEM)证明主要存在形态为红色纳米硒。结果提示PC可能是SeO32?作用的敏感靶点,Se(Ⅳ)对PC主要表现为氧化损伤,而Se(Ⅳ)被还原为红色纳米硒。     

Rectification of nomenclature for Melagraphia aethiops (Gmelin) and Diloma bicanaliculata (Dunker) (Mollusca: Trochidae)

Alterations to nomenclature for two common intertidal New Zealand ‘top shells’ necessitated by re‐examination of type material have been confused by ambiguities in the way the alterations were first presented. We draw attention to recent misinterpretations and clarify the nomenclature. Condensed synonymies that indicate names used for each species during the interregnum are given, allowing papers dealing with these trochids to be read without uncertainty as to which species were really meant by the authors.     

东山湾海水中Fe(II)和Fe(III)相互转化围隔实验研究

根据2008 年8 月与11 月在东山湾海域获得的调查资料对表层水中溶解态Fe(II)和Fe(III)含量、浮游植物叶绿素a、营养元素及其浓度等环境参数进行分析。结果表明, 夏、秋季海水中Fe(II)浓度及其在总溶解铁中所占比例均与浮游植物叶绿素a 呈正相关, 其相关系数分别为0.7959、0.9219。现场围隔实验表明, 海水中总溶解态Fe 含量在24 h 内有较大的变化, 最大减少量达到17.4%。DS2 站点海水中Fe(II)浓度及其在总溶解铁中所占比例随光照强度增加而增加。最高值与初始值相比较, 叶绿素a 较高的DS2 站点海水中Fe(II)浓度增加较叶绿素a 较低的DS5 号站点高0.053μg/L。Fe(II)和Fe(III)加富实验研究了溶解态的Fe(II)和Fe(III)在海水中相互转化。高浓度的Fe(II)在海水中被氧化成Fe(III),海水中浮游植物也会引发光还原作用使Fe(III)还原成Fe(II)。     

Determination of cadmium(II), copper(II), manganese(II) and nickel(II) species in Antarctic seawater with complexing resins

The strong species of cadmium(II), copper(II), manganese(II) and nickel(II) in an Antarctic seawater sample are investigated by a method based on the sorption of metal ions on complexing resins. The resins compete with the ligands present in the sample to combine with the metal ions. Two resins with different adsorbing strengths were used. Very stable metal complexes were investigated with the strong sorbent Chelex 100 and weaker species with the less strong resin, Amberlite CG-50. Strong species were detected for three of the considered metal ions, but not for Mn(II). Cu(II) is completely linked to species with a side reaction coefficient as high as log α_M(I) = 11.6 at pH = 7.3. The ligand concentration was found to be similar to that of the metal ion, and the conditional stability constant was around 10²⁰ M^− 1. In the considered sample, only a fraction of the metal ions Cd(II) and Ni(II) is bound to the strong ligands, with side reaction coefficients equal to log α_M(I) = 5.5 and 6.5 at pH = 7.3 for Cd(II) and Ni(II), respectively. These findings were confirmed by the test with the weaker sorbent Amberlite CG-50. It can be calculated from the sorption equilibria that neither Mn(II) nor Ni(II) is adsorbed on Amberlite CG-50 under the considered conditions and, in fact, only a negligible fraction of Mn(II) and Ni(II) was adsorbed. A noticeable fraction of Cd(II) was adsorbed on Amberlite CG-50, meaning that cadmium(II) is partially linked to weak ligands, possibly chloride, while no copper(II) was adsorbed on this resin, confirming that copper(II) is only combined in strong species. These results are similar, but not identical, to those obtained for other seawater samples examined in previous investigations.     

Se(Ⅳ)和Te(Ⅳ)对钝顶螺旋藻的急性毒性和联合毒性

用化学品对藻类毒性测试的标准试验方法,分别研究了硫属元素Se(Ⅳ)和Te(Ⅳ)单组分对钝顶螺旋藻(Spirulina platensis)的毒性效应,用相加指数法评价了Se(Ⅳ)和Te(Ⅳ)双组分对螺旋藻的联合毒性效应.结果表明,Te(Ⅳ)对螺旋藻的毒性大于Se(Ⅳ),其EC50,96h分别为125.2 mg/L和36.1 mg/L;Se(IV)和Te(Ⅳ)的联合毒性效应为拮抗作用, 其EC50,96h为103.1 mg/L.     

旋链角毛藻和小普林藻对二甲基硫和二甲巯基丙酸的释放研究

通过实验室培养研究了旋链角毛藻(Chaetoceros curvisetus Cleve)和小普林藻(Prymnesium parvum Carter)生长周期内培养液中二甲基硫(DMS)和二甲巯基丙酸(DMSP)的含量。结果表明,2种微藻均能释放DMS,但小普林藻单细胞释放的DMS浓度约是旋链角毛藻的500倍。在藻类生长的不同阶段,它们释放DMS和DMSP的能力存在较大差异,但2种藻类DMS大量释放均出现在衰亡期。同时研究了盐度对2种微藻DMS释放的影响,结果表明高盐度会促进小普林藻DMS和DMSP的释放,而对旋链角毛藻DMSP的释放未有显著影响。     

The speciation of Fe(II) and Fe(III) in natural waters

The interactions of Fe(II) and Fe(III) with the inorganic anions of natural waters have been examined using the specific interaction and ion pairing models. The specific interaction model as formulated by Pitzer is used to examine the interactions of the major components (Na⁺, Mg²⁺, Ca²⁺, K⁺, Sr²⁺, Cl⁻, SO₄⁻, HCO₃⁻, Br⁻, CO₃²⁻, B(OH)₄⁻, B(OH)₃ and CO₂) of seawater and the ion pairing model is used to account for the strong interaction of Fe(II) and Fe(III) with major and minor ligands (Cl⁻, SO₄²⁻, OH⁻, HCO₃⁻, CO₃²⁻ and HS⁻) in the waters. The model can be used to estimate the activity and speciation of iron in natural waters as a function of composition (major sea salts) and ionic strength (0 to 3 M). The measured stability constants (K_FeX^*) of Fe(II) and Fe(III) have been used to estimate the thermodynamic constants (K_FeX) and the activity coefficient of iron complexes (γ_FeX) with a number of inorganic ligands in NaClO₄ medium at various ionic strengths: In(K_FeX/γ_Feγ_X) = InK_FeX − In(γ_FeX) The activity coefficients for free ions (γ_Fe, γ_x) needed for this extrapolation have been estimated from the Pitzer equations. The activity coefficients of the ion pairs have been used to determine Pitzer parameters (B_FeX, B_FeX⁰, C_FeX^φ) for the iron complexes. These results make it possible to estimate the stability constants for the formation of Fe(II) and Fe(III) complexes over a wide range of ionic strengths and in different media. The model has been used to determine the solubility of Fe(III) in seawater as a function of pH. The results are in good agreement with the measurements of Byrne and Kester and Kuma et al. When the formation of Fe organic complexes is considered, the solubility of Fe(III) in seawater is increased by about 25%.     

Simple determination of dimethylsulfide (DMS) and dimethylsulfoniopropionate (DMSP) using solid-phase microextraction and gas chromatography-mass spectrometry

Solid-phase microextraction (SPME) is a simple, sensitive and less destructive method for the determination of dimethylsulfide (DMS) in seawater. Combined with detection by gas chromatography-mass spectrometry (GC-MS), the method had sufficient sensitivity (minimum detectable concentration of DMS was 0.05 nM), and practical levels of reproducibility (relative standard deviation ≤7%) and linearity (r ² > 0.995) over a wide concentration range (0.5 to 910 nM). The protocol developed was applied to a Sagami Bay water sample to determine concentrations of DMS and DMSP, and in situ DMSP-lyase activity.     

Diet shifts of Caribbean grunts (Haemulidae) and snappers (Lutjanidae) and the relation with nursery-to-coral reef migrations

The spatial size distribution of grunts and snappers have previously indicated the separation of juveniles in nursery habitats from the adults on the coral reef. This implies life cycle migrations from nursery habitats (such as seagrass beds and mangroves) to the coral reef. If diet shifts are related to such migrations, then the diets of these fish must change before or around the fish size at which such migrations take place. A wide size range of juveniles of two grunt species (Haemulon sciurus and Haemulon flavolineatum) and of two snapper species (Lutjanus apodus and Ocyurus chrysurus) were caught in seagrass beds and mangroves, and their gut contents identified and quantified. Regression analysis between fish size and dietary importance of small crustaceans showed a negative relationship in all four species. Positive relations were found for H. sciurus, L. apodus and O. chrysurus between fish length and the dietary importance of decapods, and for L. apodusand O. chrysurus between fish length and prey fish importance. Critical changes in the fish diets with fish size were examined by application of a Canonical Correspondence Analysis (CCA). The CCA yielded three clusters of size-classes of fishes with similar diets, and application of a Mantel test showed that each of these clusters had significantly different diets, and that each cluster diet was significantly specialised. The size at which a fish species ‘switched’ from one cluster to another was compared with size-at-maturity data and with the typical size at which these species migrate from the nursery habitats to the coral reef. H. sciurus and H. flavolineatum may be prompted to migrate from the nursery habitats to coral reef habitats because of dietary changes, or because of the development of the gonads. For L. apodus and O. chrysurus, a dietary changeover forms a more likely explanation for nursery-to-reef migrations than does sexual maturation because these species reach maturity at sizes much larger than the maximum size of individuals found in nursery habitats. Although other factors may theoretically initiate or promote the migration patterns, the results of this study indicate that ontogenetic dietary changes may crucially influence the nursery-to-coral reef migrations of these reef fish species.     

Trophic accumulation and depuration of mercury by blue crabs (Callinectes sapidus) and pink shrimp (Penaeus duorarum)

Mercury concentrations in blue crabs (Callinectes sapidus) collected from an area of mercury-contaminated sediments in Lavaca Bay, TX, USA, are more than an order of magnitude greater than concentrations in penaeid shrimp from the same area. Laboratory feeding experiments using mercury-contaminated fish as food showed that both blue crabs and pink shrimp (Penaeus duorarum) could accumulate mercury concentrations comparable to those in their food in 28 days. Calculated mercury assimilation efficiencies averaged 76% for blue crabs and 72% for pink shrimp. Significant depuration of mercury by blue crabs was not observed during a subsequent 28-day period, but pink shrimp lost mercury at a rate of about 0.012 day-1. Model calculations predict biomagnification factors of mercury of about two to three at steady state for both species. The large difference in observed concentrations of mercury in field-collected blue crabs and penaeid shrimp does not result from differences in efficiency of mercury assimilation from their food or from differences in excretion rates. It is more likely the result of differences in residence times in the contaminated area and of differences in feeding habits.     

1117号“纳沙”和1119号“尼格”风暴潮比较分析

2011年,1117号强台风“纳沙”和1119号强台风“尼格”分别在海南岛沿岸登陆,在海南岛沿岸造成不同程度的风暴潮,部分岸段最高潮位超过当地警戒潮位,给海南省造成严重的经济损失.本文分别从热带气旋特征、增水特征、灾害损失等方面进行分析,对这两次风暴潮增水过程的特征进行比较,以便为以后的风暴潮预报积累经验,更好地为我省海洋减灾防灾服务.