The Hydrolysis of Al(III) in NaCl solutions: A Model for M(II), M(III), and M(IV) Ions

Understanding the identity and stability of the hydrolysis products of metals is required in order to predict their behavior in natural aquatic systems. Despite this need, the hydrolysis constants of many metals are only known over a limited range of temperature and ionic strengths. In this paper, we show that the hydrolysis constants of 31 metals [i.e. Mn(II), Cr(III), U(IV), Pu(IV)] are nearly linearly related to the values for Al(III) over a wide range of temperatures and ionic strengths. These linear correlations allow one to make reasonable estimates for the hydrolysis constants of +2, +3, and +4 metals from 0 to 300°C in dilute solutions and 0 to 100°C to 5 m in NaCl solutions. These correlations in pure water are related to the differences between the free energies of the free ion and complexes being almost equal $$ \Updelta {\text{G}}^\circ \left( {{\text{Al}}^{3 + } } \right) - \Updelta {\text{G}}^\circ \left( {{\text{Al}}\left( {\text{OH}} \right)_{j}^{{\left( {3 - j} \right)}} } \right) \cong \Updelta {\text{G}}^\circ \left( {{\text{M}}^{n + } } \right) - \Updelta {\text{G}}^\circ \left( {{\text{M}}\left( {\text{OH}} \right)_{j}^{{\left( {n - j} \right)}} } \right) $$ The correlation at higher temperatures is a result of a similar relationship between the enthalpies of the free ions and complexes $$ \Updelta {\text{H}}^\circ \left( {{\text{Al}}^{3 + } } \right) - \Updelta {\text{H}}^\circ \left( {{\text{Al}}\left( {\text{OH}} \right)_{j}^{3 - j} } \right) \cong \Updelta {\text{H}}^\circ \left( {{\text{M}}^{n + } } \right) - \Updelta {\text{H}}^\circ \left( {{\text{M}}\left( {\text{OH}} \right)_{j}^{n - j} } \right) $$ The correlations at higher ionic strengths are the result of the ratio of the activity coefficients for Al(III) being almost equal to that of the metal. $$ \gamma \left( {{\text{M}}^{n + } } \right)/\gamma \left( {{\text{M}}\left( {\text{OH}} \right)_{j}^{n - j} } \right) \cong \gamma \left( {{\text{Al}}^{3 + } } \right)/\gamma \left( {{\text{Al}}\left( {\text{OH}} \right)_{j}^{3 - j} } \right) $$ The results of this study should be useful in examining the speciation of metals as a function of pH in natural waters (e.g. hydrothermal fresh waters and NaCl brines).     

Potential competition between hybrid striped bass (Morone saxatilis × M. americana) and striped bass (M. saxatilis) in the Cape Fear River estuary, North Carolina

Gillnet surveys from 1990 to 1992 and from 1996 to 1999 indicated a two-fold decrease in native striped bass (Morone saxatilis) populations and a concomitant two-fold increase in hybrid striped bass (Morone saxatilis × M. americana) in the Cape Fear River estuary, North Carolina. Gut content analysis indicated high diet overlap, and tagrecapture data suggested that hybrid striped bass participate in spawning migrations. These data provide circumstantial evidence that hybrid striped bass compete with striped bass for food and that they may compete for mates or habitat on the spawning grounds. Increasing abundance of adult hybrid striped bass in this system elevates the likelihood of hybrid introgression. We recommend that stocking of hybrid striped bass be terminated to preserve native striped bass populations.     

Dietary overlap between invasion ctenophora (M. leidyi ) and anchovy (C. engrauliformis) in the southern parts of Caspian Sea

Mnemiopsis leidyi, native to America, Invaded the Caspian Sea in 1999. By the end of 2000, the entire sea was accupied with them. In parallel, a sharp decline in pelagic fish such accurrred.This survey was studied the relationship between the M. leidyi and this decline. Dietary analysis was conducted on anchovy sprat (Clupeonnela engrauliformis) and M. leidyi from August 2001 to October 2002 in the coastal water in the southern parts of Caspian Sea, in Iran. M. leidyi was caught by plankton net, (the mesh size ～5 mm), at three depth at 5, 10 and 15m. Sprat was caught by fisheries boat at Babolasar fishery harbor. Samples were not fixed in M. leidyi common fixative, 96% Ethanol were used. The Schoener index analysis reflected a similar diet composition of both species, with an critical level of overlap (>89 in Babolsar samples and >84 in Noushahar samples). This competition is one of the reasons for the decline of anchovy sprat. also, the results show M. leidyi is feeding on fish eggs, but effects of this factor on anchovy population is less than feeding competition. Controlling of M. leidyi population is reducing the pressure of its invasion and the effective approach is introduces a predator to the Caspian Sea.     

Metalliferous sediments from the H.M.S. Challenger voyage (1872-1876)

The legendary cruise of H.M.S. Challenger (1872-1876) around the globe must always occupy an eminent place in the annals of oceanography, as being the first systematic attempt made on a global scale to explore the ocean. This expedition made fundamental discoveries in biology and geology which have not been surpassed by any later scientific cruise. Sediment with high content of metals (later called “metalliferous”) was among the enigmatic findings taken onboard. Although the nature of metalliferous sediments is well known today, the very first sampled sediments of this type have not been studied to date. Motivated by the historical value of Challenger’s metalliferous sediment collection we undertook an investigation addressing two questions: (1) the composition of sediments from seafloor for which we have very limited data; (2) Sr-Nd-Pb-Fe-Zn-isotope signature of these sediments collected before the substantial human impact on the ocean during the 20th century.The SE Pacific metalliferous sediments sampled by the Challenger’s explorers are of 2 types: (1) metalliferous oozes blanketing ridge crests and flanks down to the calcite compensation depth (CCD); and (2) stripped of CaCO₃ metalliferous sediments located beneath the CCD in the deeps near the mid-ocean ridges. The abiogenic part of these sediments is composed mainly of poorly-crystalline to X-ray amorphous Fe-Mn-oxyhydroxides, and an amorphous silicate phase. These sediments have geochemical features similar to those of all the other metalliferous sediments: very high Fe and Mn content (on abiogenic basis), very low Al/(Al + Fe + Mn), and high content (on abiogenic basis) of As, Ba, Be, Bi, Cd, Co, Cu, Mo, Ni, Pb, Sb, Th, Tl, U, V, W, Y, Zn and Zr. Their REE distribution patterns are similar to that of deep seawater and show weak signs of hydrothermal imprint (weak positive or no Eu anomaly).Seawater and/or terrigenous input from South America control the Sr-Nd-Pb-isotope signature of the Challenger metalliferous sediments and have almost completely obliterated any original MORB-derived hydrothermal signal. Zn isotopes are mainly contributed from seawater although other Zn sources (hydrothermal fluid and detrital aluminosilicates, barite and volcanic glass) are necessary to fully explain Zn-isotope ratios. Fe isotopes indicate relatively slow Fe²⁺ to Fe³⁺ oxidation in the non-buoyant plume, thus producing relatively lighter Fe-isotope signature of the FeOOH particles that formed the studied metalliferous sediments.     

单斜星叶石矿物的穆斯堡尔光谱学研究

本文对产于俄罗斯希宾地区的单斜星叶石进行了不同的温度条件下的穆斯堡尔光谱效应研究,通过在温度分别在298 K,180 K和80 K条件下的分析,发现单斜星叶石由2个Fe~(2 )和1个Fe~(3 )四极双峰组成,并进行了单斜星叶石中的畸变参数包括八面体键角(σ~2)和键长变量(Δ)的计算。但是,在两个畸变参数之间存在着明显的差异,将无法对它们的穆斯堡尔参数和四极双峰进行指派。本文对温度在同质异能位移和四极分裂中的作用进行了探讨,根据通过穆斯堡尔效应和f(Fe~(3 )(O))/f(Fe~(2 )(O))的平均值获得的三价铁对全铁的比值,改写了单斜星叶石的化学式。     

汶川8.0级地震地表破裂带

汶川8.0级地震的发震构造为龙门山断裂带。地震地表破裂分布在北川-映秀断裂和江油-灌县断裂上,长度分别为200km和70km。地震地表破裂表现为地表出露的地震破裂面、雁列分布的地震裂缝、地震断坎和断塞塘等。地表破裂的性质主要为右旋逆冲,最大同震位错的逆冲量和走滑量均为5.0m左右,分别位于擂鼓和虹口附近。地表破裂带的最大挤压缩短量为3.5m左右,最大宽度约为70～100m。