Anoxic nitrification: Evidence from Humber Estuary sediments (UK)

Conventional understanding of the nitrogen cycle in marine sediments has changed in recent years with the discovery of an alternative pathway for ammonia oxidation via the reduction of manganese oxides (during anoxic nitrification). In anoxic sediments, the potential for manganese oxides to serve as oxidant for nitrification may be considerable yet previous work on manganese-rich sediments has suggested anoxic nitrification may not be significant. In this study, the potential for anoxic nitrification in a range of sediment types was investigated. Laboratory incubation of sediment from three sites on the Humber Estuary, a microbially diverse environment, showed anoxic accumulation of nitrate, nitrite and dinitrogen gas, with and without the addition of synthetic manganese oxides. Incubation experiments confirmed anoxic nitrification as microbially mediated, with heat-killed controls yielding negative results. The anoxic nitrification reaction significantly depleted ammonia concentrations, and occurred simultaneously with manganese-, iron- and sulphate reduction, and methanogenesis. Taken in conjunction with other studies, results suggest anoxic nitrification may not only be dependent on total manganese concentrations but on manganese dynamics. Anoxic nitrification may be explained as a non-steady state reaction, dependent on the recent stability of a sediment system. Physical perturbation of sediments may cause the redistribution and/or introduction of manganese oxides and promote anoxic nitrification. The significance and persistence of anoxic nitrification is likely to depend on the frequency and magnitude of sediment perturbation, which explains why the reaction varies so widely across studied sites, and why it may not occur in some manganese-rich sediment.     

Origin of Fe-Ti Oxide Ores in Mafic Intrusions: Evidence from the Panzhihua Intrusion, SW China

Economic concentrations of Fe–Ti oxides occur as massive,conformable lenses or layers in the lower part of the Panzhihuaintrusion, Emeishan Large Igneous Province, SW China. Mineralchemistry, textures and QUILF equilibria indicate that oxidesin rocks of the intrusion were subjected to extensive subsolidusre-equilibration and exsolution. The primary oxide, reconstructedfrom compositions of titanomagnetite in the ores and associatedintergrowths, is an aluminous titanomagnetite (Usp₄₀) with 40wt % FeO, 34 wt % Fe₂O₃, 16·5 wt % TiO₂, 5·3 wt% Al₂O₃, 3·5 wt % MgO and 0·5 wt % MnO. This compositionis similar to the bulk composition of the oxide ore, as inferredfrom whole-rock data. This similarity strongly suggests thatthe ores formed from accumulation of titanomagnetite crystals,not from immiscible oxide melt as proposed in earlier studies.The occurrence of oxide ores in the lower parts of the Panzhihuaintrusion is best explained by settling and sorting of densetitanomagnetite in the ferrogabbroic parental magma. This magmamust have crystallized Fe–Ti oxides relatively early andabundantly, and is likely to have been enriched in Fe and Tibut poor in SiO₂. These features are consistent with fractionationof mantle-derived melts under relatively high pressures (10kbar), followed by emplacement of the residual magma at 5 kbar.This study provides definitive field and geochemical evidencethat Fe–Ti oxide ores can form by accumulation in ferrogabbro.We suggest that many other massive Fe–Ti oxide depositsmay have formed in a similar fashion and that high concentrationsof phosphorus or carbon, or periodic fluctuation of fO₂ in themagma, are of secondary importance in ore formation. KEY WORDS: ELIP; Fe–Ti oxide ore; layered intrusion; Panzhihua; QUILF     

Geoacoustic Inversion via Genetic Algorithm and Its Application to Manganese Sediment Identification

An acoustic inversion method using a wide-band signal and two near field receivers is proposed and applied to multiple layered seabed models including a manganese sediment. The inversion problem can be formulated into a probabilistic model comprised of signals, a forward model, and additive noise. The forward model simulates wide-band signals, such as chirp signals, and is chosen to be the source-waveletconvolution plane wave modeling method. The wavelet matching technique, using weighted least-squares fitting, estimates the sediment sound-speed and thickness on which determination of the possible numerical ranges for a priori uniform distribution is based. The genetic algorithm is applied to a global optimization problem to find a maximum a posteriori solution for determined a priori search space. Here the object function is defined by an L 2 norm of the difference between measured and modeled signals. Not only the marginal pdf but also its statistics are calculated by numerical evaluation of integrals using the samples selected during importance sampling process of the genetic algorithm.     

Manganese and iron distributions off central California influenced by upwelling and shelf width

In July 2002, a combination of underway mapping and discrete profiles revealed significant along-shore variability in the concentrations of manganese and iron in the vicinity of Monterey Bay, California. Both metals had lower concentrations in surface waters south of Monterey Bay, where the shelf is about 2.5 km wide, than north of Monterey Bay, where the shelf is about 10 km wide. During non-upwelling conditions over the northern broad shelf, dissolvable iron concentrations measured underway in surface waters reached 3.5 nmol L⁻¹ and dissolved manganese reached 25 nmol L⁻¹. In contrast, during non-upwelling conditions over the southern narrow shelf, dissolvable iron concentrations in surface waters were less than 1 nmol L⁻¹ and dissolved manganese concentrations were less than 5 nmol L⁻¹. A pair of vertical profiles at 1000 m water depth collected during an upwelling event showed dissolved manganese concentrations of 10 decreasing to 2 nmol L⁻¹, and dissolvable iron concentrations of 12–20 nmol L⁻¹ in the upper 100 m in the north, compared to 3.5–2 nmol L⁻¹ Mn and 0.6 nmol L⁻¹ Fe in the upper 100 m in the south, suggesting the effect of shelf width influences the chemistry of waters beyond the shelf.These observations are consistent with current understanding of the mechanism of iron supply to coastal upwelling systems: Iron from shelf sediments, predominantly associated with particles greater than 20 μm, is brought to the surface during upwelling conditions. We hypothesize that manganese oxides are brought to the surface with upwelling and are then reduced to dissolved manganese, perhaps by photoreduction, following a lag after upwelling.Greater phytoplankton biomass, primary productivity, and nutrient drawdown were observed over the broad shelf, consistent with the greater supply of iron. Incubation experiments conducted 20 km offshore in both regions, during a period of wind relaxation, confirm the potential of these sites to become limited by iron. There was no additional growth response when copper, manganese or cobalt was added in addition to iron. The growth response of surface water incubated with bottom sediment (4 nmol L⁻¹ dissolvable Fe) was slightly greater than in control incubations, but less than in the presence of 4 nmol L⁻¹ dissolved iron. This may indicate that dissolvable iron is not as bioavailable as dissolved iron, although the influence of additional inhibitory elements in the sediment cannot be ruled out.     

水样及生物体内微量锌、锰、硒的极谱催化波同时测定

本文提出了在酒石酸盐-乙二胺-高氯酸-亚硫酸钠-高碘酸钾-EDTA体系中同时测定微量锌、锰、硒的极谱催化波，波峰敏锐，波形稳定。Zn2 浓度在0．4～40μg／dm3，Mn2 浓度在1．6～80μg／dm3，Se（Ⅳ）浓度在0．02～3．0μg／dm3范围内浓度与峰电流呈线性关系。取天然水样平行12份测定，变异系数在10％以内。     

Kinetics of redox cycling of iron coupled with fulvic acid

The kinetics of conversion of iron(III) (hydr)oxides to ferrous iron mediated by fulvic acid have been investigated in order to improve the understanding of the redox cycling of iron at the oxic-anoxic boundary in natural waters. Under the conditions similar to natural waters, fulvic acid is able to reduce the iron(III) (hydr)oxide. The kinetics of the reaction depend on the reactivity of iron(III) (hydr)oxides and the reducing power of the fulvic acid. The rate of reaction is 60 nm/h obtained under following conditions: total concentration of Fe(III) 1.0 × 10^–4 M, pH 7.5, fulvic acid 5 mg/L. The rate is considered as a net result of reduction and oxidation in the > Fe^III-OH/Fe(II) wheel coupled with fulvic acid. In a real natural water system, reductants other than fulvic acid may be of importance. The results obtained in the laboratory, however, provide evidence that the Fe(OH)₃(s)/Fe(II) redox couple is able to act as an electron-transfer mediator for the oxidation of natural organic substances, such as fulvic acid by molecular oxygen either in the absence of microorganisms or as a supplement to microbial activity.     

A multivariate statistical and geostatistical study on the geochemistry of allochtonous karst bauxite deposits in Hungary

A geochemical evaluation of the Szc-Halimba-Kisld area, Hungary, covering an area of more than 200 km² is presented using different statistical and geostatistical methods. The study area is a representative example of allochtonous karst bauxite accumulation. The three groups of deposits studied here have been explored and mined since 1950. Several thousand boreholes have been drilled, and bauxite cores were analyzed for the five main chemical components. A total of 80,000 pleces of analytical data were processed, followed by a geological examination of borehole logs and of mining excavations.The quantitative geochemical evaluation of the data set led to both geochemical and practical results: The geochemical behavior of the allochtonous, clastic karst bauxite deposits differs essentially from that of the autochtonous and parautochtonous ones, as well as that of the lateritic bauxite deposits. The deposits of the study area can be split into several subsequent geochemical-sedimentological units, each representing an event of bauxite transport and accumulation. Clear regional patterns can be revealed in the composition of these units. The geostatistically measured chemical variability of the geochemical units is rather different, the lowest units showing the smallest variability. The interrelations of the main chemical components are weaker and more irregular in the studied deposits than in the autochtonous lateritic bauxite deposits. Additional local genetic features, such as transport routes, can be delineated by the methods applied. Within each deposit, local changes of chemical composition and of its variability can be determined more precisely. These results can be used in bauxite prospecting and exploration, because areas of high or low bauxite quality can be predicted.     

Speciation of adsorbed arsenate on the surface of hydrous iron oxide

Adsorption of arsenate on hydrous iron oxide is an important process controlling geochemical cycling of arsenic in environment as well as the fate of arsenic-bearing mining wastes. The widely accepted view on the mechanism of adsorption is that arsenate is adsorbed via bidentate binuclear inner-sphere complexation. In this study, we characterized the arsenate-hydrous iron oxide sorption solids synthesized at pH=3-8 using Fourier transformed infrared spectroscopy （FTIR） and X-ray diffraction （XRD）. It has been determined that poorly crystalline ferric arsenate developed on the surface of iron oxide when arsenate was sorbed at acidic pH, while at alkaline pH the adsorption of arsenate was via bidentate complexation.     

First-Order Chemistry in the Surface-Flux Layer

We have discussed the behavior of a non-conserved scalar in the stationary, horizontally homogeneous, neutral surface-flux layer and, on the basis of conventional second-order closure, derived analytic expressions for flux and for mean concentration of a gas, subjected to a first-order removal process. The analytic flux solution showed a clear deviation from the constant flux, characterizing a conserved scalar in the surface-flux layer. It decreases with height and is reduced by an order of magnitude of the surface flux at a height equal to about the typical mean distance a molecule can travel before destruction. The predicted mean concentration profile, however, shows only a small deviation from the logarithmic behavior of a conserved scalar. The solution is consistent with assuming a flux-gradient relationship with a turbulent diffusivity corrected by the Damköhler ratio, the ratio of a characteristic turbulent time scale and the scalar mean lifetime. We show that if we use only first-order closure and neglect the effect of the Damköhler ratio on the turbulent diffusivity we obtain another analytic solution for the profiles of the flux and the mean concentration which, from an experimental point of view, is indistinguishable from the first analytic solution. We have discussed two cases where the model should apply, namely NO which, by night, is irreversibly destroyed by interaction with mainly O₃ and the radioactive ²²⁰Rn. Only in the last case was it possible to find data to shed light on the validity of our predictions. The agreement seemed such that a falsification of our model was impossible. It is shown how the model can be used to predict the surface flux of ²²⁰Rn from measured concentration profiles.     

ICP—AES法同时测定高纯氧化钇中稀土及非稀土杂质元素方法研究

本文提出了用ＩＣＰ－ＡＥＳ法直接同时测定高纯氧化钇中１４个稀土和１６个非稀土杂质元素的分析方法，对被测元素的 谱线、氧化钇基本及背景影响进行了研究，用标准加入法测出氧化钇基准中的微量杂质元素，消除了由于忽略基准中的杂质元素含量给高纯氧化钇分析测定带来的误差，同时对工作条件进行了优化。方法中各被测元素的检出限为0.003～1.31ug/g，能够满足生产过程中的质量控制及进出口商品检验