The oxidation states of cobalt and selected metals in Pacific ferromanganese nodules

A study of the oxidation states of metals in selected Pacific ferromanganese nodules by x-ray photoelectron spectroscopy (XPS) indicates the presence of Co(III), Pb(II), Pb(IV), Fe(III) and Ti(IV). These findings are based on measurements of core electron binding energies and an evaluation of the core electron shake-up satellite features.     

X-ray photoelectron spectroscopic study of ferromanganese nodules: Chemical speciation for selected transition metals

Analysis of manganese nodules, with emphasis on speciation of transition metal components, has been carried out using x-ray photoelectron spectroscopy. In nodules containing predominantly δ-MnO₂, Co(III) was identified from an examination of XPS photopeak structural features. In a nodule composed of todorokite, Cu(II) and Ni(II) were detected in oxide environments, but the quantity of cobalt was insufficient to be studied in detail.     

太平洋海底富钴结壳中的烃类有机质及其成因意义

用气相色谱-质谱(GC-MS)联测方法测定了中西太平洋海底海山富钴结壳中的可溶有机质,对其丰度、生源构成、沉积环境、成熟度等方面进行了初步的探讨.富钴结壳的烃类生物标志化合物大多具成熟烃特征,个别具低成熟烃特点."A"/C高达9.81～21.15,显示出运移烃的特征;藿烷C31-R(S JR)为0.43～0.46,Tm/(Tm Ts)为0.40～0.59,C30αβ藿烷/(αβ藿烷 βα莫烷)为0.85～0.89,C29αβ藿烷/(αβ藿烷 βα莫烷)为0.81～0.85,c29甾烷20S/(20S 20R)为0.45～0.60,从而计算出Rsc(%)为0.73%～0.81%,个别达到1.06%;C29αββ/(αββ ααα)为0.35～0.42.甾烷丰度顺序为C29甾烷＞C27甾烷＞C28甾烷,同时检出了孕甾烷和4-甲基甾烷,重排甾烷三角图显示该有机质为Ⅱ型.Pr/Ph值介于0.35～0.82,显示植烷优势.说明烃类形成于强还原环境.链状烷烃、类异戊二烯烷烃、萜烷、甾烷化合物的组成和分布都说明茵藻类低等水生生物和陆源高等植物混合生源输入.洋底热液活动是富钴结壳中有机质热演化的重要热源.有机质在特定的海底条件下生成,并被运移到海山上,通过扩散和浸粢由外层进入结壳.     

Trace element associations with Fe- and Mn-oxides in soil nodules: Comparison of selective dissolution with electron probe microanalysis

Selective dissolution methods have been largely used to get insight on trace element association with solid phases. Modern instrumental techniques offer many tools to test the validity of selective dissolution methods and should be systematically used to this end. The association of trace elements with Fe- and Mn-oxides in soil nodules has been studied here by electron probe microanalysis. The results were compared with findings from an earlier study on selective dissolution of the same nodules by hydroxylamine hydrochloride, acidified hydrogen peroxide, and Na-citrate-bicarbonate-dithionite. Electron probe microanalysis results were consistent with previous findings using selective dissolution and showed that P, As and Cr were mainly present in Fe-oxides, while Co was mainly associated with Mn-oxide phases. These results support the applicability of the studied selective dissolution methods for fractionation of trace elements in soils and sediments containing appreciable amounts of Fe and Mn-oxide phases.     

陆源碎屑沉积物中沉积成因锶钡的选择性提取新技术

正1研究目的(Objective)目前大家进行陆源碎屑沉积物海陆相沉积环境判别时通常采用的是全样总量分析获得的锶钡比来判别沉积环境。全样总量分析主要有两类方法,一类是X荧光光谱法(分熔片法和压片法),另一类为消解液的等离子光谱或质谱法(分熔融法和酸解法)。由于全样总量分析的锶钡既包含有赋存     

A hybrid model using machine learning methods and GIS for potential rockfall source identification from airborne laser scanning data

The main objectives of this paper are to design and evaluate a hybrid approach based on Gaussian mixture model (GMM) and random forest (RF) for detecting rockfall source areas using airborne laser scanning data. The former model was used to calculate automatically slope angle thresholds for different type of landslides such as shallow, translational, rotational, rotational-translational, complex, debris flow, and rockfalls. After calculating the slope angle thresholds, a homogenous morphometric land use area (HMLA) was constructed to improve the performance of the model computations and reduce the sensitivity of the model to the variations in different conditioning factors. After that, the support vector machine (SVM) was applied in addition to backward elimination (BE) to select and rank the conditioning factors considering the type of landslides. Then, different machine learning methods [artificial neural network (ANN), logistic regression (LR), and random forest (RF) were trained with the selected best factors and previously prepared inventory datasets. The best fit method (RF) was then used to generate the probability maps and then the source areas were detected by combining the slope raster (reclassified according to the thresholds found by the GMM model) and the probability maps. The accuracy assessment shows that the proposed hybrid model could detect the potential rockfalls with an accuracy of 0.92 based on training data and 0.96 on validation data. Overall, the proposed model is an efficient model for identifying rockfall source areas in the presence of other types of landslides with an accepted generalization performance.     

Speciation analysis of metals （Tl, Cd and Pb） in Tl-containing pyrite and its cinder from Yunfu Mine, China, by ICP-MS with sequential extraction

The speciation of heavy metals such as thallium, cadmium and lead existing in pyrite and pyrite cinder was analyzed by ICP-MS with a sequential extraction procedure. The distribution patterns of these metals including exchangeable, reducible, oxidizable and residual fractions were obtained. Tl, Cd and Pb in pyrite and pyrite cinder samples from each extraction step were determined by inductively coupled plasma mass spectrometry (ICP-MS). Under the optimized instrumental conditions, detection limits of Tl, Cd and Pb in different matrices were within the range of 0.006–0.07 μg/L, and the relative standard deviations ranged from 0.8% to 1.2%. The accuracy of Tl, Cd and Pb determination was checked by analyzing two certified reference materials. The results demonstrate that trace Tl, Cd and Pb in the samples can be accurately determined. The sequential extraction results revealed that the percent contents of Tl, Cd and Pb in exchangeable, reducible and oxidizable fractions in pyrite cinder are different from those in pyrite and in pyrite cinder. Tl, Cd and Pb mostly are distributed in residual fraction. Therefore, the mobility of metals in pyrite is higher than that in pyrite cinder. Although distributions of Tl, Cd and Pb in the non-residual fraction are not dominant in pyrite cinder, the total concentrations of them could not be ignored. Consequently, attention must be paid to the risk of potential pollution by pyrite cinder.     

Analysis and characterization of samples from sedimentary strata with correlations to indicate the potential for hydrocarbons

The Rock-Eval pyrolysis and TOC analysis have been widely used to evaluate the source rock quality. The atomic H/C ratio of kerogen, however, has been overlooked in source rock evaluation. In this study, coal and carbonaceous samples, including 26 from northwestern Taiwan, 12 from China, and 4 from the United States were analyzed, and integrated with 157 published data, to explore the significance of atomic H/C ratio as a parameter of source rock evaluation. Two different linear trends were observed in the cross-plot of S ₁ versus S ₂. Field outcropped shale or C-shale exhibits a steeper slope compared to that of coal samples which can be attributed to the compositional difference in their organic material. A rather strong positive correlation for H% versus S ₂ illustrates the contribution of H-containing macerals, especially exinite. Organic matters in the samples studied are of type II/III kerogen based on the relationship between HI and T _max. The H/C ratio, as well as the HI, S ₁, and S ₂, generally decreases with the maturity increasing. The H/C ratio decreases slightly from 1.1 to 0.7 with the maturity increasing from R _o 0.55 to 0.85%. Samples with H/C ratio in this range show significant change in certain other geochemical parameters (e.g. HI, S ₁, S ₂, S ₁ + S ₂, S ₁/(S ₁ + S ₂), S ₁/TOC, (S ₁ + S ₂)/TOC, T _max). The (S ₁ + S ₂)/TOC ratio (defined as QI) was used as an indicator of the hydrocarbon potential. The QI, HI, and H/C ratio show a certain correlation, all increasing accordingly. The QI of the samples analyzed in this study is approximately 100–380 (mgHC/gTOC), similar to that of most humic coals for oil and gas generation. Samples with R _o value lower than 0.55% always show significant variation in their HI, ranging from 80 to 520 mgHC/gTOC. It is inferred that hydrocarbon potential started from R _o 0.55% and atomic H/C ratio 1.1 in this study.     

Comparison of methods for the removal of organic carbon and extraction of chromium, iron and manganese from an estuarine sediment standard and sediment from the Calcasieu River estuary, Louisiana, U.S.A.

U.S. National Bureau of Standards (NBS) estuarine sediment 1646 from the Chesapeake Bay, Maryland, and surface sediment collected at two sites in the Calcasieu River estuary, Louisiana, were used to evaluate the dilute hydrochloric acid extraction of Cr, Fe and Mn from air-dried and freeze-dried samples that had been treated by one of three methods to remove organic carbon. The three methods for the oxidation and removal of organic carbon were: (1) 30% hydrogen peroxide; (2) 30% hydrogen peroxide plus 0.25 mM pyrophosphate; and (3) plasma oxidation (low-temperature ashing). There was no statistically significant difference at the 95% confidence level between air- and freeze-dried samples with respect to the percent of organic carbon removed by the three methods. Generally, there was no statistically significant difference at the 95% confidence level between air- and freeze-dried samples with respect to the concentration of Cr, Fe and Mn that was extracted, regardless of the extraction technique that was used. Hydrogen peroxide plus pyrophosphate removed the most organic carbon from sediment collected at the site in the Calcasieu River that was upstream from industrial outfalls. Plasma oxidation removed the most organic carbon from the sediment collected at a site in the Calcasieu River close to industrial outfalls and from the NBS estuarine sediment sample. Plasma oxidation merits further study as a treatment for removal of organic carbon. Operational parameters can be chosen to limit the plasma oxidation of pyrite which, unlike other Fe species, will not be dissolved by dilute hydrochloric acid. Preservation of pyrite allows the positive identification of Fe present as pyrite in sediments.     

Sampling and analytical procedures for the determination of VOCs released into air from natural and anthropogenic sources: A comparison between SPME (Solid Phase Micro Extraction) and ST (Solid Trap) methods

In the present study, two sampling and analytical methods for VOC determination in fumarolic exhalations related to hydrothermal-magmatic reservoirs in volcanic and geothermal areas and biogas released from waste landfills were compared: (a) Solid Traps (STs), consisting of three phase (Carboxen B, Carboxen C and Carbosieve S111) absorbent stainless steel tubes and (b) Solid Phase Micro Extraction (SPME) fibers, composed of DiVinylBenzene (DVB), Carboxen and PolyDimethylSiloxane. These techniques were applied to pre-concentrate VOCs discharged from: (i) low-to-high temperature fumaroles collected at Vulcano Island, Phlegrean Fields (Italy), and Nisyros Island (Greece), (ii) recovery wells in a solid waste disposal site located near Florence (Italy). A glass condensing system cooled with water was used to collect the dry fraction of the fumarolic gases, in order to allow more efficient VOC absorption avoiding any interference by water vapor and acidic gases, such as SO₂, H₂S, HF and HCl, typically present at relatively high concentrations in these fluids. Up to 37 organic species, in the range of 40–400 m/z, were determined by coupling gas chromatography to mass spectrometry (GC–MS). This study shows that the VOC compositions of fumaroles and biogas determined via SPME and ST are largely consistent and can be applied to the analysis of VOCs in gases released from different natural and anthropogenic environments. The SPME method is rapid and simple and more appropriate for volcanic and geothermal emissions, where VOCs are present at relatively high concentrations and prolonged gas sampling may be hazardous for the operator. The ST method, allowing the collection of large quantities of sample, is to be preferred to analyze the VOC composition of fluids from diffuse emissions and air, where these compounds are present at relatively low concentrations.     

Geochemistry of Tertiary tholeiites and picrites from Qeqertarssuaq (Disko Island) and Nuussuaq, West Greenland with implications for the mineral potential of comagmatic intrusions

Tertiary continental flood basalts on Qeqertarssuaq and Nuussuaq in West Greenland contain ～3?km of picrites and variably contaminated tholeiites. The picrites are in the Naujánguit member of the Vaïgat Formation and they have 7–29?wt% MgO, La/Sm?=?0.9–2.1, and ¹⁴³Nd/¹⁴⁴Nd?=?0.51263–0.51307. They appear to have crystallised from high-Mg parental magmas (14.4–16.4?wt% MgO) with isotope and trace element ratios similar to recent Icelandic picrites. Discrete horizons of tholeiites, including the Asûk and?Kûgánguaq, have elevated SiO₂ (50–58 wt%), La/Sm?=?3–7, ⁸⁷Sr/⁸⁶Sr?=?0.70550–0.71224, and low ¹⁴³Nd/¹⁴⁴Nd?=?0.51234–0.51174. These lavas have low Cu and Ni abundances (typically 10–50?ppm Ni or Cu), and in the case of the Asûk on Qeqertarssuaq, they contain droplets of native iron. The low Cu and Ni contents are attributed to scavenging by magmatic sulphides formed in response to crustal contamination of picritic magmas. Two contamination trends are recognised, one to a sediment end-member with high Th/Nb and Archaean model Nd ages, and the other to a meta-igneous component with high La/Sm, low Th/Nb and Rb/Nb, and Proterozoic source ages. Overall, ²⁰⁶Pb/²⁰⁴Pb varies from 16.47–21.68. Both contamination trends are associated with low Cu and Ni, and high SiO₂, and it is argued that the magmatic sulphides were triggered by the increases in silica, rather than simply by the introduction of additional crustal-derived sulphur. Geochemically, the Asûk and Kûgánguaq rocks resemble the most contaminated Nadezhdinsky lavas of the Siberian Trap, which are widely regarded as the source of the Ni and Cu mineralisation in the giant Noril'sk deposits. Mass balance considerations indicate that the parental liquids to the contaminated magmas contained sufficient Ni, Cu, S and platinum group elements to form substantial magmatic sulphide deposits. However, unlike the lavas at Noril'sk, the contaminated (low Cu and Ni) West Greenland basalts are in isolated units with no evidence for a gradual recovery in Ni and Cu abundances with height in the lava column. Comparison with Noril'sk suggests that although significant quantities of metals were scavenged by sulphides in West Greenland, the metal contents of the sulphides may not have been upgraded by continued interaction with subsequent magma batches.