唐山地震的超晚期强余震估计

根据华北历史地震的重复性和免疫性，认为在唐山周围８５ｋｍ，２００年内，对６级地震具有一定的免疫性；在研究了唐山地震序列自身的衰减规律后，认为在今后几十几强余震的最大活动水平为５级，发生６级以上土地震的可能性很小。     

Adsorption of REE(III)-humate complexes onto MnO2: Experimental evidence for cerium anomaly and lanthanide tetrad effect suppression

Experiments were conducted to evaluate the impact of organic complexation on the development of Ce anomalies and the lanthanide tetrad effect during the adsorption of rare-earth elements (REE) onto MnO₂. Two types of aqueous solutions—NaCl and NaNO₃—were tested at pH 5 and 7.5. Time-series experiments indicate that a steady-state is reached within less than 10 h when REE occur as free inorganic species, whereas steady state is not reached before 10 d when REE occur as REE-humate complexes. The distribution coefficients (K_d^REE) between suspended MnO₂ and solution show no or only very weak positive Ce anomaly or lanthanide tetrad effect when REE occur as humate complexes, unlike the results obtained in experiments with REE occurring as free inorganic species. Monitoring of dissolved organic carbon (DOC) concentrations show that log K_d^REE_organic/K_d^DOC ratios are close to 1.0, implying that the REE and humate remain bound to each other upon adsorption. Most likely, the Ce anomaly reduction/suppression in the organic experiments arises from a combination of two processes: (i) inability of MnO₂ to oxidize Ce(III) because of shielding of MnO₂ surfaces by humate molecules and (ii) Ce(IV) cannot be preferentially removed from solution due to quantitative complexation of the REE by organic matter. We suggest that the lack of lanthanide tetrad effect arises because the adsorption of REE-humate complexes onto MnO₂ occurs dominantly via the humate side of the complexes (anionic adsorption), thereby preventing expression of the differences in Racah parameters for 4f electron repulsion between REE and the oxide surface. The results presented here explain why, despite the development of strongly oxidizing conditions and the presence of MnO₂ in the aquifer, no (or insignificant) negative Ce anomalies are observed in organic-rich waters. The present study demonstrates experimentally that the Ce anomaly cannot be used as a reliable proxy of redox conditions in organic-rich waters or in precipitates formed at equilibrium with organic-rich waters.     

Origin of salinity in a multilayered aquifer with high salinization vulnerability

The Kaluvelly watershed is a coastal area (Tamil Nadu, India) where water abstraction has resulted in a dramatic fall in the level of the water table and a piezometric depression in the most exploited aquifer, the Vanur aquifer. In addition, intensification/mechanization of agriculture may have affected the quality of recharge water. An initial hydrodynamic study showed that the Vanur aquifer is highly vulnerable to salinization due to potential seawater intrusion, and our aim was to determine the source of salinity recorded in the groundwater of this multilayered aquifer. Our approach involved the use of existing boreholes and of a moderate number of samples, with the aim of developing appropriate water resource management techniques. Major element, ¹⁸O/¹⁶O, ²H/¹H and ⁸⁷Sr/⁸⁶Sr, ratios were measured in rainwater, surface water and groundwater collected during five sampling campaigns over a 2‐year period. Geochemical data indicate that the Vanur aquifer is recharged and that small mixings between aquifers fluctuate according to monsoon intensity. There was no evidence of seawater intrusion. The range of recorded salinity originated mainly from water–rock interaction but a disconnection of some deeper parts of the aquifer was apparent. Strontium isotopic ratios in the recharge area suggest an anthropogenic influence, possibly related to fertilizer use. A high SO₄/Cl ratio was observed in the aquifer; in the deeper parts, the influence of a formation containing lignite is hypothesized, whereas near the surface, sulphate may partly originate from fertilizer use and fossil fuel combustion. Water isotopic data suggest that the origin of precipitation in this region has been unchanged for several hundreds or thousands of years. Copyright © 2011 John Wiley & Sons, Ltd.     

Metal loading effect on rare earth element binding to humic acid: Experimental and modelling evidence

The effect of metal loading on the binding of rare earth elements (REE) to humic acid (HA) was studied by combining ultrafiltration and Inductively Coupled Plasma Mass Spectrometry techniques. REE-HA complexation experiments were performed at pH 3 for REE/C molar ratios ranging from ca 4 × 10⁻⁴ to 2.7 × 10⁻². Results show that the relative amount of REE bound to HA strongly increases with decreasing REE/C. A middle-REE (MREE) downward concavity is shown by patterns at high metal loading, whereas patterns at low metal loading display a regular increase from La to Lu. Humic Ion Model VI modelling are close to the experimental data variations, provided that (i) the ΔLK₂ parameter (i.e. the Model VI parameter taken into account the presence of strong but low density binding sites) is allowed to increase regularly from La to Lu (from 1.1 to 2.1) and (ii) the published log K_MA values (i.e. the REE-HA binding constants specific to Model VI) are slightly modified, in particular with respect to heavy REE. Modelling approach provided evidence that patterns with varying REE/C likely arises because REE binding to HA occurs through two types of binding sites in different density: (i) a few strong sites that preferentially complex the heavy REE and thus control the atterns at low REE/C; (ii) a larger amount of weaker binding sites that preferentially complex the middle-REE and thus control the pattern at high REE/C. Hence, metal loading exerts a major effect on HA-mediated REE binding, which could explain the diversity of published conditional constants for REE binding with HA. A literature survey suggests that the few strong sites activated at low REE/C could be multidentate carboxylic sites, or perhaps N-, or P-functional groups. Finally, an examination of the literature field data proposed that the described loading effect could account for much of the variation in REE patterns observed in natural organic-rich waters (DOC > 5 mg L⁻¹ and 4 ? pH ? 7).     

Origin and evolution of fluids from mud volcanoes in the Barbados accretionary complex

A large collection of fluids (54 interstitial fluids and four expelled fluids) were sampled at the Manon site, at the outer edge of the Barbados accretionary complex. These warm fluids (up to 20°C) are expelled by sub-marine (5000 mbsl) mud volcanoes consisting of diapirs (unchanneled flow) and diatremes (channeled).Chlorine stable isotope ratios of these fluids were measured by IRMS with a reproducibility of ± 0.05‰ (1σ) versus SMOC (Standard Mean Ocean Chloride).A large range of δ³⁷Cl between −5.3‰ and +0.1‰ is observed. Data from each volcanic structure describe a mixing between seawater and a low-δ³⁷Cl fluid. The whole set of data is interpreted as the result of a mixing between two deep components and seawater. The two deep fluids are chemically distinct (e.g., in Ca, Mg, K, Li, Sr and Br contents and Br/Cl ratio). They display low and significantly different ⁸⁷Sr/⁸⁶Sr ratios (0.707790 and 0.707892, respectively) and δ³⁷Cl values (−4.51 and −5.24‰, respectively).Physicochemical processes such as mineralogical transformation, diffusion, compaction or ion filtration are known to fractionate chlorine stable isotopes and can produce fluids with negative δ³⁷Cl values. Ion filtration due to sediment compaction appears to be the more likely process to explain the negative δ³⁷Cl values observed at the Manon site. A model for the generation of these signatures is proposed where a residual negative δ³⁷Cl fluid reservoir is created at the bottom of the prism or the sediment pile. Further compaction/fracturing and/or dewatering of the slab may flush out these fluids and focus them towards the décollement zone. Mixing between the fluids and ultimately with seawater and water released during gas hydrate destabilizations may explain the data set within the individual cores and between the different structures.     

Hypoxia in Manila Bay, Philippines during the northeast monsoon

Herein we present results from one of the first extensive bay-wide oceanographic surveys of Manila Bay, wherein 31 stations were sampled during the northeast monsoon (cold and dry season). A band of hypoxic bottom water (dissolved oxygen<2.8 mg/L) spanned the midsection of the bay from east to west. Bottom nitrate concentrations (5.7-16.8 μM; avg. 11.1 μM) and total organic carbon values in sediments (1.7-3.1%; avg. 2.4%) were high in the midsection, which coincided with the band of hypoxic bottom water. Physical processes and site-specific accumulation of organic material likely lead to hypoxic conditions in Manila Bay, even during the northeast monsoon period when the water column is relatively well mixed. The results of this study complement the previously reported widespread hypoxia that occurs during the rainy season. Thus, hypoxia may be pervasive in the bay throughout the year, although it varies in intensity and spatial extent.     

Discrimination between different water bodies from a multilayered aquifer (Kaluvelly watershed,India): Trace element signature

In the multilayered aquifer of Kaluvelly (India), comprising various sedimentary layers overlying a charnockitic basement, concentrations of trace elements were measured in aquifer formations and in groundwaters to identify geochemical tracers for water bodies. The two main sandstones (Cuddalore and Vanur) originate from the charnockites and the Cuddalore sandstone has experienced lateritization. In the studied area, two charnockite end-members were identified: a dioritic and a granitic one. Mineralogical composition and whole-rock Ti concentrations confirmed the charnockite which displayed the granitic composition as the parent rock of the two sandstones. Titanium distribution indicates that the Cuddalore sandstone originates from a more intense weathering of the parent material than the Vanur sandstone. Despite extensive differences in trace element contents recorded in aquifer formations, only a few trace elements were suitable to distinguish the water bodies. Among soluble elements, Li (in the Vanur aquifer) and Ba (in the charnockite and carbonaceous aquifers) can be used as tracers. As the input of these elements in solution is mainly regulated by the available stock, for a given mineralogical origin there is a direct link between the aquifer formation composition and water signature. With the exception of As, concentrations of redox-sensitive elements were not preserved during pumping because of oxidation, preventing their use as tracers. Low-mobility elements such as La, Ce, Th, Zr, Nb, Hf, or Ta were too insoluble to be detected in waters and/or to record the aquifer formation signature. Their input in solution was not regulated by the available stock but by the dissolution rate of rock-forming minerals. Only Ti can be used to distinguish between two out of the three aquifers (charnockite and Vanur). The specific behavior of Ti recorded in these waters may be linked to rutile inclusions within plagioclases and to the influence of climate on Ti solubility.     

Competitive binding of REE to humic acid and manganese oxide: Impact of reaction kinetics on development of cerium anomaly and REE adsorption

The competitive binding of rare earth elements (REE) to purified humic acid (HA) and MnO₂ was studied experimentally using various HA/MnO₂ ratios over a range of pH (3 to 8). MnO₂, humic acid and REE solutions were simultaneously mixed to investigate the kinetics of the competitive reactions. Aqueous REE–HA complex is the dominant species whatever the experiment time, pH and HA/MnO₂ ratio. The value of the distribution coefficients between MnO₂ and solution (log K_d^Ree/Mno₂) increases with the HA/MnO₂ ratio, indicating that part of the REE–HA complexes are adsorbed onto MnO₂. The development of a Ce anomaly appears strongly limited in comparison with inorganic experimental conditions. Throughout the experimental run time, for HA/MnO₂ ratios of less than 0.4, MnO₂ acts as a competitor leading to a partial dissociation of the REE–HA complex. The majority of the dissociated REE is readsorbed onto the MnO₂ surface. The readsorption of REE is expressed by an increased Ce anomaly on the log K_d^Ree/Mno₂ pattern as well as a change in shape of the coefficient distribution of REE between soluble HA and solution pattern (log K_d^Ree/HA decrease for the heavy rare earth elements — HREE). Thus, REE are not only bound to MnO₂ as a REE–HA complex, but also as REE(III). Moreover, the competition between HA and MnO₂ for REE binding is shown to be higher at low pH (< 6) and low DOC/Mn ratio. This study partially confirms previous work that demonstrated the control of REE adsorption by organic matter, while shedding more light on the impact of pH as well as complexation reaction competition on long-term REE partitioning between solid surface and organic solutions. The latter point is important as regards to REE speciation under conditions typical of rock and/or mineral alteration.     

Mobilization and redistribution of major and trace elements in two weathering profiles developed on serpentinites in the Lomié ultramafic complex, South-East Cameroon

The behaviour of major and trace elements have been studied along two serpentinite weathering profiles located in the Kongo-Nkamouna and Mang North sites of the Lomié ultramafic complex.The serpentinites are characterized by high SiO₂ and MgO contents, very low trace, rare earth and platinum-group element contents. Lanthanide and PGE contents are higher in the Nkamouna sample than in Mang North. Normalized REE patterns according to the CI chondrites reveal that: (i) all REE are below chondrites abundances in the Mang North sample; (ii) the (La/Yb)_N ratio value is higher in the Nkamouna sample (23.72) than in the Mang one (1.78), this confirms the slightly more weathered nature of the Nkamouna sample. Normalized PGE patterns according to the same CI chondrites reveal a negative Pt anomaly in the Mang sample. The Nkamouna sample is characterized by a flat normalized PGE pattern.All element contents increase highly from the parent rock to the coarse saprolite.In the weathering profiles, Fe₂O₃ contents decrease from the bottom to the top contrarily to Al₂O₃, SiO₂ and TiO₂. The contents of alkali and alkaline oxides are under detection limit.Concerning trace elements, Cr, Ni, Co, Cu, Zn and Sc decrease considerably from the bottom to the top while Zr, Th, U, Be, Sb, Sn, W, Ta, Sr, Rb, Hf, Y, Li, Ga, Nb and Pb increase towards the clayey surface soil. Chromium, Ni and Co contents are high in the weathered materials in particular in the saprolite zone and in the nodules.REE contents are high in the weathered materials, particularly in Nkamouna. Their concentrations decrease along both profiles. Light REE are more abundant than heavy REE. Normalized REE patterns according to the parent rock reveal positive Ce anomalies in all the weathered materials and negative Eu anomalies only at the bottom of the coarse saprolite (Nkamouna site). Positive Ce anomalies are higher in the nodular horizon of both profiles. An additional calculation method of lanthanide anomalies, using NASC data, confirms positive Ce anomalies ([Ce/Ce^*]_NASC = 1.15 to 60.68) in several weathered materials except in nodules ([Ce/Ce^*]_NASC = 0.76) of the upper nodular horizon (Nkamouna profile). The (La/Yb)_N ratios values are lower in the Nkamouna profile than in Mang site.PGE are more abundant in the weathered materials than in the parent rock. The highest contents are obtained in the coarse saprolite and in the nodules. The elements with high contents along both profiles are Pt (63–70 ppb), Ru (49–52 ppb) and Ir (41 ppb). Normalized PGE patterns show positive Pt anomalies and negative Ru anomalies.The mass balance evaluation, using thorium as immobile element, reveals that:

– major elements have been depleted along the weathering profile, except for Fe, Mn and Ti that have been enriched even only in the coarse saprolite;

– all the trace elements have been depleted along both profiles, except for Cr, Co, Zn, Sc, Cu, Ba, Y, Ga, U and Nb that have been enriched in the coarse saprolite;

– rare earth elements have been abundantly accumulated in the coarse saprolite, before their depletion towards the top of the profiles;

– platinum-group elements have been abundantly accumulated in the coarse saprolite but have been depleted towards the clayey surface soil.

Moreover, from a pedogenetical point of view, this study shows that the weathering profiles are autochtonous, except in the upper part of the soils where some allochtonous materials are revealed by the presence of zircon grains.