Kinetics of phosphate adsorption by iron oxyhydroxides in aqueous systems

The rate of uptake of phosphate onto synthetic Fe(III)- and Fe(II)-derived oxyhydroxides has been studied using reaction conditions similar to those encountered in natural waters. Kinetic analyses were carried out on the adsorption profiles and both first-order and second-order conditional rate constants were obtained. The temperature dependence of some of the rate constants was investigated and corresponding apparent activation energies calculated. Similar experiments and analyses were undertaken using Fe from natural sources and in general the conditional rate constants obtained in seawater were in agreement with the synthetic ones. The results of this study are of value when comparing the time scales of adsorption processes in natural waters with the time scales of mixing and advection.     

甘南毕家山铅锌矿床地质特征与成因

该矿床由两种类型矿化组成:(1)与所谓“微石英岩”密切共生的成层碎屑矿;(2)层状矿下伏石灰岩顶部的网脉矿。矿石硫化物在同位素组成上与围岩中的黄铁矿显然不同,其δ~(34)S值( 15至 18)表明可能是海水来源的,由海水硫酸离子在较高温度下无机还原而成。矿石中的碳酸盐矿物以较低的δ~(13)C和较高的δ~(18)O值不同于围岩石灰岩,前者表明可能有深成碳参加,后者表明成矿流体可能在较高温度下与硅酸盐岩石达到了同位素平衡。氧化硅的δ~(18)O值很重,落入海相燧石的变化范围。区域内没有火山活动的确切证据,以海水来源为主的成矿流体可能是沿分开不同地层小区的区域性断裂循环并被加热的。     

Stable isotope constraints on the Al2SiO5'triple-point' rocks from the Proterozoic Priest pluton contact aureole, New Mexico, USA

The Priest pluton contact aureole in the Manzano Mountains, central New Mexico preserves evidence for upper amphibolite contact metamorphism and localized retrograde hydrothermal alteration associated with intrusion of the 1.42 Ga Priest pluton. Quartz–garnet and quartz–sillimanite oxygen isotope fractionations in pelitic schist document an increase in the temperatures of metamorphism from 540 °C, at a distance of 1 km from the pluton, to 690 °C at the contact with the pluton. Comparison of calculated temperature estimates with one‐dimensional thermal modelling suggests that background temperatures between 300 and 350 °C existed at the time of intrusion of the Priest pluton. Fibrolite is found within 300 m of the Priest pluton in pelitic and aluminous schist metamorphosed at temperatures >580 °C. Coexisting fibrolite and garnet in pelitic schist are in oxygen isotope equilibrium, suggesting these minerals were stable reaction products during peak metamorphism. The fibrolite‐in isograd is coincident with the staurolite‐out isograd in pelitic schist, and K‐feldspar is not observed with the first occurrence of fibrolite. This suggests that the breakdown of staurolite and not the second sillimanite reaction controls fibrolite growth in staurolite‐bearing pelitic schist. Muscovite‐rich aluminous schist locally preserves the Al₂SiO₅ polymorph triple‐point assemblage – kyanite, andalusite and fibrolite. Andalusite and fibrolite, but not kyanite, are in isotopic equilibrium in the aluminous schist. Co‐nucleation of fibrolite and andalusite at 580 °C in the presence of muscovite and absence of K‐feldspar suggests that univariant growth of andalusite and fibrolite occurred. Kyanite growth occurred during an earlier regional metamorphic event at a temperature nearly 80 °C lower than andalusite and fibrolite growth. Quartz–muscovite fractionations in hydrothermally altered pelitic schist and quartzite are small or negative, suggesting that late isotopic exchange between externally derived fluids and muscovite, but not quartz, occurred after peak contact metamorphism and that hydrothermal alteration in pelitic schist and quartzite occurred below the closure temperature of oxygen self diffusion in quartz (<500 °C).     

Estimation of Fe3+ from electron microprobe analyses: observations on calcic amphibole and chlorite

ABSTRACT Metabasites and metagreywackes from the Pelona and Rand Schists of southern California were analysed using three different electron microprobes. For all three instruments, the estimated Fe³⁺ contents of calcic amphibole, chlorite and epidote are positively correlated. For some samples, there is an additional correlation between high estimated Fe³⁺ and the presence of magnetite. These results imply that microprobe analyses can be used to discern relative differences in Fe³⁺. However, microprobe data and calculations on the sensitivity of the correction procedures to systematic analytical errors indicate that estimated values of Fe³⁺ are not significant in an absolute sense. Thus, estimates of Fe³⁺ are meaningful when comparing samples analysed with a single microprobe, but must be used with caution when comparing analyses obtained on more than one probe.     

Properties of iron at the Earth's core conditions

Summary. The phase diagram of iron up to 330 GPa is solved using the experimental data of static high pressure (up to 11 GPa) and the experimental data of shock wave data (up to 250 GPa). A solution for the highest triple point is found ( P = 280 GPa and T = 5760 K) by imposing the thermodynamic constraints of triple points. This pressure of the triple point is less than the pressure of the inner core–outer core boundary of the Earth. These results indicate that the density of iron at the inner core–outer core boundary pressure is close to 13 g cm⁻³, which lies close to the seismic solutions of the Earth at that pressure. It is thus concluded that the Earth's inner core is very likely to be virtually pure iron in its hexagonal close packed (hcp) phase.
It is shown that four properties of the Earth's inner core determined from seismology are close in value to the corresponding properties of hcp iron at inner core conditions: density, bulk modulus, longitudinal velocity, and Poisson's ratio. The density–pressure profile of hcp iron at inner core conditions matches the density–pressure profile of the inner core as determined by seismic methods, within the spread of values given by recent seismic models.
This indicates that the Earth is slowly cooling, the Earth's inner core is growing by crystallization, and the impurities of the core are concentrated in the outer core. The calculated temperature at the Earth's centre is 6450 K.     

Isotopic evidence of TSR origin for natural gas bearing high H<Subscript>2</Subscript>S contents within the Feixianguan Formation of the northeastern Sichuan Basin,southwestern China

The northeastern area of Sichuan Basin, southwestern China, is the area with the maximal reserve of natural gas containing higher hydrogen sulphide (H₂S) that has been found among the petroliferous basins of China, with the proven and controlled gas reserve of more than 200 billion cubic meters. These gas pools, with higher H₂S contents averaging 9%, some 17%, are mainly distributed on structural belts of Dukouhe, Tieshanpo, Luojiazhai, Puguang, etc., while the oolitic-shoal dolomite of the Triassic Feixianguan Fm. (T₁f) is the reservoir. Although many scholars regard the plentiful accumulation of H₂S within the deep carbonate reservoir as the result of Thermochemical Sulfate Reduction (TSR), however, the process of TSR as well as its residual geological and geochemical evidence is still not quite clear. Based on the carbon isotopic analysis of carbonate strata and secondary calcite, etc., together with the analysis of sulfur isotopes within H₂S, sulphur, gypsum, iron pyrites, etc., as well as other aspects including the natural gas composition, carbon isotopes of hydrocarbons reservoir petrology, etc., it has been proved that the above natural gas is a product of TSR. The H₂S, sulphur and calcite result from the participation of TSR reactions by hydrocarbon gas. During the process for hydrocarbons being consumed due to TSR, the carbons within the hydrocarbon gas participate in the reactions and finally are transferred into the secondary calcite, and become the carbon source of secondary calcite, consequently causing the carbon isotopes of the secondary calcite to be lower (−18.2‰). As for both the intermediate product of TSR, i.e. sulfur, and its final products, i.e. H₂S and iron pyrites, their sulfur elements are all sourced from the sulfate within the Feixianguan Fm. During the fractional processes of sulfur isotopes, the bond energy leads to the ³²S being released firstly, and the earlier it is released, the lower δ ³⁴S values for the generated sulphide (H₂S) or sulfur will be. However, for the anhydrite that participates in reactions, the higher the reaction degree, the more ³²S is released, while the less ³²S remains and the more δ ³⁴S is increased. The testing results have proved the process of the dynamic fractionation of sulfur isotopes.     

Behaviour of iron,manganese, phosphate and humic acid during mixing in a Delaware salt marsh creek

The mixing behaviour of iron, manganese, phosphate and humic acid in a Delaware salt marsh creek was studied using field data, laboratory mixing experiments, and geochemical mass balance equations. Property-salinity diagrams for field data indicated that the removal of iron is 56–70% in the 0–10‰ salinity range. A proposed mechanism of removal is the flocculation of colloidal iron, perhaps with humic acid. Phosphate, however, undergoes 195% addition in the same low salinity region, which may be due to release of phosphate from resuspended sediments. Dissolved manganese is conserved, as is humic acid throughout the salt marsh mixing zone. Within the uncertainty of the data the maximum possible removal of humic acid is 23%.Laboratory mixing experiments that simulated salt marsh mixing along the same salinity gradient as observed in the field (5–25‰) showed only small-scale additions and removals compared to the field results. Such small-scale changes occurred largely at salinities >10‰ in the laboratory experiments, whereas most removals and additions occurred at salinities <10‰ in the field. Mixing studies also showed little difference between prefiltered and unfiltered mixes. The studies suggest that simple mixing of salt marsh waters, with or without suspended material, does not strongly influence the observed behaviour of dissolved constituents in salt marshes, and that other processes (e.g. sediment or intertidal exchange) must dominate their behaviour.     

济南张马屯铁矿帷幕注浆堵水工程简介

济南张马屯铁矿安全生产30年,其根本保证是通过帷幕注浆建立起了一条长效稳定的地下“拦水大坝”。该技术不仅具有极高的安全效益和经济效益,同时具有保护地下水资源的社会效益。该项技术适用范围广、工艺成熟、易于实施,应该作为深井大水矿山地下水治理的主要技术方法予以推广应用。     

Paleolimnological investigations of anthropogenic environmental change in Lake Tanganyika: VII. Carbonate isotope geochemistry as a record of riverine runoff

Evaporation dominates the removal of water from Lake Tanganyika, and therefore the oxygen isotope composition of lake water has become very positive in comparison to the waters entering the lake. The surface water in Lake Tanganyika has remained relatively unchanged over the last 30 years with a seasonal range of +3.2 to +3.5 VSMOW. Water from small rivers entering the lake seems to have a ¹⁸O value between –3.5 and –4.0, based on scattered measurements. The two largest catchments emptying into the lake deliver water that has a ¹⁸O value between these two extremes. This large contrast is the basis of a model presented here that attempts to reconstruct the history of runoff intensity based on the ¹⁸O of carbonate shells from Lake Tanganyika cores. In order to use biogenic carbonates to monitor changes in the ¹⁸O of mixing-zone water, however, the oxygen isotope fractionation between water and shell carbonate must be well understood. The relatively invariant environmental conditions of the lake allow us to constrain the fractionation of both oxygen and carbon isotope ratios. Although molluskan aragonitic shell ¹⁸O values are in agreement with published mineral-water fractionations, ostracode calcite is 1.2 more positive than that of inorganic calcite precipitated under similar conditions. Ostracode shell ¹⁸O data from two cores from central Lake Tanganyika suggest that runoff decreased in the first half of this millennium and has increased in the last century. This conclusion is poorly constrained, however, and much more work needs to be done on stable isotope variation in both the waters and carbonates of Lake Tanganyika. We also compared the ¹³C of shells against predicted values based solely on the ¹³C of lake water dissolved inorganic carbon (DIC). The ostracode Mecynocypria opaca is the only ostracode or mollusk that falls within the predicted range. This suggests that M. opaca has potential for reconstructing the carbon isotope ratio of DIC in Lake Tanganyika, and may be a useful tool in the study of the history of the lakes productivity and carbon cycle.     

Assessment of Workers’ Contamination Caused by Air Pollution Exposure in Industry Using Biomonitors

The workers health service is guided to look for risks. There is not an evaluation of the onset of the disease linked to a long-term exposure to low levels of toxic agents. Besides, there are few records of the level of metal concentration in the environmental air in industry, as well as few records of the level of contamination of factory workers. To assess the level of pollution in workplace, galvanising industry was chosen as the object of this study. The worker exposure and contamination levels were assessed by means of airborne particulate matter collected in air filters and biomonitors. The analysis of the air filter, hair and toenail samples were carried out by Instrumental Neutron Activation Analysis, and urine samples by Graphite Furnace Atomic Absorption Spectrophotometry. The statistical multivariate analysis and ANOVA methods were applied to elemental concentration. Copper and iron elements were highlighted as the main contributors on the differentiation of the classes. The results point out the effectiveness of biomonitors in occupational studies.