Rare earths,other trace elements and iron in Luna 20 samples

The results of the analysis by neutron activation of six samples from the Luna 20 mission and one sample of < 1 mm fines from Apollo 16 are reported. The concentrations of the rare-earth elements (REE) in the samples of fines from Luna 20 and Apollo 16 are less than those found for corresponding materials from the mare areas but a negative Eu anomaly is still present. The concentrations of the REE in fines from Luna 20 are only about two-thirds as great as in the sample of Apollo 16 fines, but the concentrations of Co, Sc and Cr are greater by factors ranging from 1.5 to 2.3.     

Experimental evidence for mobility of Zr and other trace elements in soils

A Soxhlet extraction was carried out over a period of 27 d on a column comprising 3 cm of quartz overlain by 4 cm of soil from the B horizon and then 1 cm of soil from the A horizon of a granitic podzol. Major and trace elements were leached from the column and accumulated in a reservoir at the base of the column. Total loss of elements from the soil over the course of the experiment ranged from 0.002 to 1 wt% with major elements and the light and heavy rare earth elements (REE) showing the largest percentage losses. Zirconium (0.002%) and then Al (0.008%) showed the lowest percentage loss. The light REE were leached out of the soil preferentially to the mid REE. All elements showed accumulation, by a factor of 2 to 11, in the quartz layers at the base of the column, particularly in the upper first 1 cm of the quartz. Major elements were leached from the column at a rate of 0.02 to 0.59 μmol h⁻¹ whereas Zr, Nd, Sm, Gd, Dy, Rb, and Sr were leached at the rate of 0.5 to 30 × 10⁻⁶ μmol h⁻¹. Concentrations of other REE in the reservoir increased over the duration of the experiment, but they were poorly correlated with time, so leaching rates were not calculated. Normalization of the major element leaching rates to take into account the constant flushing of water through the column, the average annual rainfall in the Allt a’Mharcaidh catchment in Scotland from where the soil was sampled, and the cross-sectional area of the soil in the column, together with the temperature of the soil in the column (70°C) compared with the average annual temperature of the Allt a’Mharcaidh catchment (5.7°C), gave major element release rates from the soil of 0.002 to 0.97 mEq m⁻² yr⁻¹ (depending on the choice of E_a, the dissolution activation energy), which are generally less than those measured in the field of 0.1 to 40.9 mEq m⁻² yr⁻¹.Calculations showed that despite the redistribution and loss of Zr from the column, assumptions of Zr mobility would have had a negligible effect on calculated element release rates of Na, Ca, Fe, and Mg. However, significant underestimates of the release of K (5%), Ti (57%), Al (5%), and Si (10%) as well as some trace elements (e.g., Nd, 23%; Rb, 54%; Sr, 24%) would have occurred. Concentrations of Ca and Sr leached from the column correlated well (RSQ = 0.93, p < 0.01), supporting the idea of the use of Sr release as a proxy for Ca release in weathering rate calculations. The release rates and percentage loss of REE from the soil varied between elements indicating that REE distribution patterns of rocks and soils may not be preserved in drainage waters.     

Experimental study of the incorporation of Li, Sc, Al and other trace elements into olivine

We performed a series of synthesis experiments at 1 atm pressure to investigate the substitution mechanisms of 1+ and 3+ ions into olivine. Forsterite crystals were grown from bulk compositions that contained the element of interest (e.g. Li) and different amounts of additional single trace elements. By working at constant (major element) liquid composition and temperature we eliminated all compositional effects other than those due to the trace elements. Mineral-melt pairs were then analysed to determine the compositional-dependence of the partition coefficient (D), which corresponds to , and where [element] refers to weight concentration of the element in the respective phase.We find that Li forms a stable coupled substitution with Sc and, at above ∼500 ppm Sc in the crystal, Li⁺ and Sc³⁺ ions form an ordered neutral complex ([LiSc]). This complex dissociates at lower trace element concentrations and a second, concentration-independent, mechanism begins to dominate. This second solution mechanism is most likely 2Li⁺ ⇔ Mg²⁺ where one of the Li atoms is in an interstitial position in the crystal lattice. Natural olivines show Li contents slightly greater than Sc (on an atomic basis), indicating that both substitution mechanisms are significant. Unlike Sc, Al does not appear to form a stable complex with Li in the olivine structure.Sodium is highly incompatible in olivine with of ∼0.00015-0.03. Olivine-liquid partitioning of Na⁺ is independent of Sc³⁺ or Al³⁺ concentration. This indicates that the coupled substitution of Na⁺ with any 3+ ions is unlikely. Instead, the relevant substitution mechanism appears to be 2Na⁺ ⇔ Mg²⁺. Although independent of 3+ ion concentration, is inversely correlated with the Li concentration of both melts and crystals, implying that Na competes (unsuccessfully) with Li to replace Mg in the olivine structure.Aluminium is highly incompatible in forsterite . Values of are similar for all phase pairs synthesised from starting materials containing between 10 and 100,000 ppm Al. This suggests that Al is principally incorporated in forsterite by replacing one Mg and one Si atom , where the Al atoms on octahedral (Mg) and tetrahedral (Si) sites are dissociated from one another.The incorporation of gallium into forsterite is influenced by the presence of Li. Where Li concentration in the crystal is much greater than that of Ga (on an atomic basis) we find an excellent correlation between and melt Li content. This relationship indicates that Ga³⁺ and Li⁺ replace 2Mg²⁺ on octahedral sites and that the Ga and Li atoms are, like Sc and Li, strongly associated in the crystal structure.The mechanism by which scandium is incorporated into forsterite is strongly governed by the presence Li. As discussed above, ordered complexes form readily in forsterite in Li-rich experiments. Under Li-absent but Sc-rich conditions (Sc in the crystal >∼500 ppm), is proportional to the concentration of Sc in the melt. This indicates that Sc incorporation is charge-balanced by the formation of magnesium vacancies , and that both species are associated . At lower Sc concentrations (<500 ppm in the crystal), the concentration-dependence of partitioning indicates that the complexes dissociate.Our results demonstrate that partitioning of 1+ and 3+ ions into olivine is complex and involves a range of point defects which yield strongly composition-dependent crystal-melt partition coefficients. Since physical and chemical properties of natural olivine, such as diffusion of ⁶Li and ⁷Li and H₂O solubility, depend on the concentrations of the defects identified in this study, our results provide an important insight into how determining substitution mechanisms can improve our understanding of large-scale mantle processes and properties.     

Mobilisation of arsenic and other trace elements in fluviolacustrine aquifers of the Huhhot Basin,Inner Mongolia

Observed As concentrations in groundwater from boreholes and wells in the Huhhot Basin of Inner Mongolia, northern China, range between <1 μg l⁻¹ and 1480 μg l⁻¹. The aquifers are composed of Quaternary (largely Holocene) lacustrine and fluvial sediments. High concentrations are found in groundwater from both shallow and deep boreholes as well as from some dug wells (well depths ranging between <10 m and 400 m). Populations from the affected areas experience a number of As-related health problems, the most notable of which are skin lesions (keratosis, melanosis, skin cancer) but with internal cancers (lung and bladder cancer) also having been reported. In both the shallow and deep aquifers, groundwaters evolve down the flow gradient from oxidising conditions along the basin margins to reducing conditions in the low-lying central part of the basin. High As concentrations occur in anaerobic groundwaters from this low-lying area and are associated with moderately high dissolved Fe as well as high Mn, NH₄, dissolved organic C (DOC), HCO₃ and P concentrations. Many of the deep groundwaters have particularly enriched DOC concentrations (up to 30 mg l⁻¹) and are often brown as a result of the high concentrations of organic acid. In the reducing groundwaters, inorganic As(III) constitutes typically more than 60% of the total dissolved As. The highest As concentrations tend to be found in groundwater with low SO₄ concentrations and indicate that As mobilisation occurs under strongly reducing conditions, where SO₄ reduction has been an active process. High concentrations of Fe, Mn, NH₄, HCO₃ and P are a common feature of reducing high-As groundwater provinces (e.g. Bangladesh, West Bengal). High concentrations of organic acid (humic, fulvic acid) are not a universal feature of such aquifers, but have been found in groundwaters from Taiwan and Hungary for example. The observed range of total As concentrations in sediments is 3–29 mg kg⁻¹ (n=12) and the concentrations correlate positively with total Fe. Up to 30% of the As is oxalate-extractable and taken to be associated largely with Fe oxides. The release of As into solution under the reducing conditions is believed to be by desorption coupled with reductive dissolution of the Fe oxide minerals. The association of dissolved As with constituents such as HCO₃, DOC and P may be a coincidence related to the prevalent reducing conditions and slow groundwater flow, but they may also be directly involved because of their competition with As for binding sites on the Fe oxides. The Huhhot groundwaters also have some high concentrations of dissolved U (up to 53 μg l⁻¹) and F⁻ (up to 6.8 mg l⁻¹). In contrast to As, U occurs predominantly under the more oxidising conditions along the basin margins. Fluoride occurs dominantly in the shallow groundwaters which have Na and HCO₃ as the dominant ions. The combination of slow flow of groundwater and the young age of the aquifer sediments are also considered potentially important causes of the high dissolved As concentrations observed as the sediments are likely to contain newly-formed and reactive minerals and have not been well flushed since burial.     

Influence of fluorine on the enrichment of high field strength trace elements in granitic rocks

The solubilities of zircon, rutile, manganocolumbite (MnNb₂O₆), manganotantalite (MnTa₂O₆), and the rare earth phosphates LaPO₄, GdPO₄, and YbPO₄ in water-saturated haplogranitic melts containing 0–6 wt.% F were measured at 800° C and 2 kbar. The melt compositions investigated differ only in their F content, the proportions of Na, K, Al, and Si are identical in all experiments. While the solubilities of the rare earth phosphates are independent of F, the solubilities of all other minerals studied strongly increase with F. The TiO₂ content of haplogranitic melt in equilibrium with rutile increases linearly from 0.26 wt.% without F to 0.47 wt.% for melts containing 6 wt.% F. Over the same range of F concentrations, the ZrO₂ content of the melt in equilibrium with zircon increases with the square of the F content from less than 0.01 wt.% to 0.25 wt.%. The linear increase for rutile and the quadratic relationship for zircon suggest a complexing mechanism. Probably nonbridging oxygen atoms (NBO) expelled from coordination with Al by reaction with F form complexes with Ti and Zr, the ratio of NBO: metal cation being 1:1 for Ti, and 2:1 for Zr. Direct complexing by F is also a possibility. As titanium oxide phases and zircon are major sinks for HFS elements such as Ti, Nb, Ta, Zr, Hf, Th and REE in granites, their increased solubility in the presence of F favors the enrichment of these elements in residual mels. The Nb and Ta content of rutile in granitic pegmatites is due to extended solid solution of rutile with columbite group minerals, such as manganocolumbite and manganotantalite. The solubility of these components also increases with F, MnTa₂O₆ being more soluble than MnNb₂O₆. Rutile fractionation could therefore account for the increase in Ta/Nb frequently observed in highly differentiated granites. The solubility of the rare earth phosphates increases strongly from LaPO₄ to GdPO₄ to YbPO₄, which explains the enrichment of heavy rare earth elements in highly evolved granites. In the presence of F, many HFS elements will be highly incompatible in granitic systems. Therefore, in a suite of granitic rocks generated by differentiation from the same source magma, a strong correlation should exist between HFS elements and F. However, because of the influence of F on the solubility of refractory phases such as zircon, a similar correlation could also result from different batches of magma containing different amounts of F equilibrating with the same refractory phase.     

Distribution Characteristics of Gold and Other Trace Elements in the Proterozoic Lengjiaxi Group,Northeastern Hunan Province

Systematic geochemical studies of the Proterozoic Lengjiaxi Group in northeastern Hunan Province suggest that the Lengjiaxi Group is a Au-As-Sb-W association-type Au-bearing turbidite formation.The contents of Au,As,Sb,W,Cr,Mn,Pb and Zn in the turbidite formation are more than two times as high as the average contents of trace elements in the upper continental crust.The low abundance of Ag and the close correlation between Au and As are two important characteristic features.In the Au-bearing turbidite formation the enrichment of gold is due to the extensive occurrence of Au-bearing pyrites.Higher contents of Au,W,Sb and Ag in the greywacke indicate that they also exist in the form of heavy minerals.Au,Ag,As,Sb,W and REE in the Au-bearing turbidite formation have a close genetic relation with the chemistry of the gold deposits.     

Distribution of arsenic and other trace elements in the Holocene sediments of the Meghna River Delta, Bangladesh

Geochemical study of the Holocene sediments of the Meghna River Delta, Chandpur, Bangladesh was conducted to investigate the distribution of arsenic and related trace and major elements. The work carried out includes analyses of core sediments and provenance study by rare earth element (REE) analysis. Results showed that the cores pass downward from silty clays and clays into fine to medium sands. The uppermost 3 m of the core sediments are oxidized [average oxidation reduction potential (ORP) + 230 mV], and the ORP values gradually become negative with depths (−45 to −170 mV), indicating anoxic conditions prevail in the Meghna sediments. The REE patterns of all lithotypes in the study areas are similar and are comparable to the average upper continental crust. Arsenic and other trace elements (Pb, Zn, Cu, Ni, and Cr) have greater concentrations in the silts and clays compared to those in the sands. Positive correlation between As and Fe was found in the sediments, indicating As may be adsorbed on Fe oxides in aquifer sediments.     

白云岩风化剖面元素地球化学特征:对黔中九架炉组“三稀金属”富集机制的启示

黔中早石炭世九架炉组铝土矿含矿岩系富集Ti、Li、Sc、V、Ga、Nb、Ta、Zr、Hf、Th和稀土(REEs)等"三稀金属",具有成为独立矿床或伴生资源的潜力。这些元素大部分与九架炉组共有同一母岩,且富集程度受母岩的成分和风化作用控制。本研究选取九架炉组母岩乌当娄山关群白云岩和纳雍牛蹄塘组泥质白云岩的现代风化剖面为研究对象,研究元素在风化作用过程中的迁移特征及分布规律,进而为九架炉组微量元素的富集机制提供启示。研究获得以下认识:1)依据剖面结构、ZrHf、Nb-Ta、Y-Ho二元图特征及REE配分曲线和Eu/Eu*值的相似性表明研究区土层主要来源于基底或母岩的风化; 2)白云岩风化成土过程中Si、Fe、Cr、As、Sb、Ti、Nb、Ta、Zr、Hf、Th、REEs等元素化学性质相对稳定,富集程度较高,而Ca、Mg、Na、K、Sr、P、Mo、Cd等元素化学性质活泼,容易淋失亏损; 3)纳雍剖面REEs~(3+)和Ca~(2+)半径差与REEs富集系数相关性良好,表明碳酸盐岩风化过程中,含钙矿物磷灰石是稀土元素分配的重要控制因素; 4)九架炉组的母岩也是Ti、Li、Sc、V、Ga、Nb、Ta、Zr、Hf、Th等微量元素的主要物质来源,母岩风化过程中,这些微量元素首先在副矿物、黏土矿物、铝矿物及磷灰石等矿物相中初步富集,之后随风化碎屑物一起沉积形成微量元素超常富集地层; 5)纳雍剖面地表和地下水提供了部分P、Be、Zn、Sb、Pb、Y及REEs来源,指示水体迁入作用也是九架炉组REEs富集的重要原因。研究表明黔中九架炉组微量元素的来源较复杂,风化-沉积过程中,化学性质稳定的元素残留在风化碎屑物中并被搬运-沉积在负地形中,而化学性质活泼的元素首先被带入水体,在沉积-成岩过程中特定条件下发生二次富集作用(例如次生矿物的形成及吸附)形成微量元素富集的地层。     

Anhydrous partial melting of MORB pyrolite and other peridotite compositions at 10 kbar: Implications for the origin of primitive MORB glasses

Summary Anhydrous partial melting experiments on four peridotite compositions have been conducted at 10 kbar providing a relatively internally consistent set of data on the character of primary melts expected from the oceanic upper mantle in the mid-ocean ridge setting. The four peridotite compositions are: MORB pyrolite (considered to be suitable for the production of primitive (Mg#0.68) MORB glasses at 10 kbar), Hawaiian pyrolite (representative of enriched upper mantle), Tinaquillo lherzolite (representative of more depleted upper mantle), and the spinel lherzolite KLB-1 which is a suitable composition for the production of primitive MORB glasses. The equilibrium liquids were determined by sandwich experiments. The primitive MORB glass DSDP 3-18-7-1 was used in experiments using MORB pyrolite and KLB-1, while a calculated 10 kbar liquid composition fromJaques andGreen (1980) was used in experiments with Hawaiian pyrolite and Tinaquillo lherzolite. The results of the experiments are used to test a 10 kbar melt model for the generation of primitive MORB glasses, which are parental magmas to typical MORB compositions. The melt compositions from the four peridotites studied are significantly different from primitive MORB glasses in major element chemistry and plot away from the field of primitive MORB glasses in the CIPW molecular normative Basalt tetrahedron. The results indicate that primitive MORB glasses are derivative compositions lying on olivine fractionation lines from picritic parents, which themselves are primary magmas at pressures greater than 10 kbar. The results of this study are integrated with previous 10 kbar experimental studies.

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Wasserfreie partielle aufschmelzung von MORB pyrolit und andere peridotit-zusammensetzungen bei 10 kbar: bedeutung für die entstehung primitiver MORB gläser

Zusammenfassung Vier Peridotit-Zusammensetzungen wurden bei 10 kbar unter wasserfreien Bedingungen partiell aufgeschmolzen, und die Ergebnisse mit möglichen primitiven Schmelzen Mittel-Ozeanischer Rücken verglichen.Die folgenden perioditischen Zusammensetzungen wurden untersucht: MORB pyrolite [mögliche Ausgangszusammensetzung für primitive (Mg# > 0.68) MORB-Glaszusammensetzungen bei 10 kbar], Hawaiian pyrolite (representativ für angereicherten Oberen Mantel); Tinaquillo lherzolite (representativ für verarmten' Oberen Mantel) und spinel lherzolite, KLB-1 (im Gleichgewicht mit primitiver MORB-Glaszusammensetzung). Die Schmelzen im Gleichgewicht mit diesen Ausgangszusammensetzungen wurden mittels Sandwich-Experimenten ermittelt.Die primitive MORB-Glaszusammensetzung DSDP 3-18-7-1 wurde mit MORB pyrolite und KLB-1 equilibriert, während eine Modell-Zusammensetzung vonJaques and Green (1980) in Verbindung mit Hawaiian pyrolite und Tinaquillo lherzolite vermischt wurde. Die Resultate der Experimente werden mit einem 10 kbar Aufschmelzungsmodell zur Entstehung primitiver MORB-Gläser verglichen. Die Schmelzen im Gleichgewicht mit den vier Peridotit-Ausgangszusammensetzungen unterscheiden sich wesentlich von primitiven MORB-Gläsern, sowohl hinsichtlich ihrer Hauptelemente als auch ihrer Plot-Parameter im Basalttetraeder. Primitive MORB-Glaszusammensetzungen stellen keine primären Schmelzen dar, sondern sind durch Olivinfraktionierung von primitiven Magmen abzuleiten. Die Resultate dieser Untersuchungen werden mit früheren 10 kbar Experimenten verglichen.

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With 10 Figures     

Geochemical study of arsenic and other trace elements in groundwater and sediments of the Old Brahmaputra River Plain,Bangladesh

The geochemical study of groundwaters and core sediments from the Old Brahmaputra plain of Bangladesh was conducted to investigate the distribution of arsenic and related trace elements. Groundwaters from tube wells are characterized by pH of 6.4–7.4, dissolved oxygen (DO) of 0.8–1.8 mg/l, Ca contents of 5–50 mg/l, and Fe contents of 0.2–12.9 mg/l. Arsenic concentrations ranged from 8 to 251 μg/l, with an average value of 63 μg/l. A strong positive correlation exists between As and Fe (r ² = 0.802; p = 0.001) concentrations in groundwater. The stratigraphic sequences in the cores consist of yellowish silty clays at top, passing downward into grayish to yellowish clays and sands. The uppermost 3 m and lower parts (from 13 to 31 m) of the core sediments are oxidized (average oxidation reduction potential (ORP) +170 and +220 mV, respectively), and the ORP values gradually become negative from 3 to 13 m depths (−35 to −180 mV), indicating that anoxic conditions prevail in the shallow aquifers of the Brahmaputra plain. Age determinations suggest that clay horizons at ~10 m depth were deposited at around 2,000 and 5,000 years BP (¹⁴C ages) during the transgressive phase of sea-level change. Elevated concentrations of As, Pb, Zn, Cu, Ni, Cr, and V are present in the silts and clays, probably due to adsorption onto clay particles. Significant concentrations of As occur in black peat and peaty sediments at depths between 9 and 13 m. A strong positive correlation between As and Fe was found in the sediments, indicating As may be adsorbed onto Fe oxides in aquifer sediments.     

Seasonal variability in response of estuarine phytoplankton communities to stress: Linkages between toxic trace elements and nutrient enrichment

We examined individual and interactive effects of two stressors—nutrients (nitrogen [N] and phosphorus [P]) and trace elements (a mix of arsenic [As], copper [Cu], and cadmium [Cd], and in a second experiment also zinc [Zn] and nickel [Ni])—on phytoplankton of the mesohaline Patuxent River, a tributary of Chesapeake Bay. Experiments were conducted in twenty 1-m³ mesocosms. Four mesocosm runs used two levels of nutrient loadings (0.7–1.0 × ambient N loading and enriched to 1.3–1.6 × ambient N loading) crossed with two levels of trace elements (ambient and enriched approximately 2–5 × higher than ambient concentrations) crossed with five progressive levels of ecosystem complexity. To examine seasonal patterns of responses to stressors, data from these experiments were combined with results of a similar experiment conducted during 1996 (Breitburg et al. 1999a). A second mesocosm experiment examined effects of individual and mixed trace elements, both alone and in combination with nutrients, to further examine which nutrient-trace element interactions were important. Nutrients consistently increased phytoplankton productivity and biomass. Most of the increased biomass was created by large centric diatoms, which increased the mean cell size of the phytoplankton community. Trace element additions decreased phytoplankton productivity and biomass, as well as the contribution of large centric diatoms to phytoplankton biomass. When both trace elements and nutrients were added, trace elements reduced nutrient stimulation. Although the magnitude of the response to nutrient additions tended to be somewhat greater in spring, the seasonal patterns of trace element effects, and nutrient-trace element interactions were far more striking with significant responses restricted to spring mesocosm runs. The second experiment indicated that both As and Cu were more inhibitory to phytoplankton in spring than in summer, but As was more inhibitory in the low nutrient treatments and Cu was more inhibitory in the nutrient enrichment treatments. The potential for strong seasonal patterns and high temporal variability in stressor effects and multiple stressor interactiosn will require close attention in the design and interpretation of management-relevant research and monitoring and may indicate the need for seasonally varying management strategies.     

Groundwater contamination with arsenic and other trace elements in an area of the pampa,province of Córdoba,Argentina

A geochemical study of groundwater of the pampa in the province of Córdoba, Argentina, was performed; the area covered approximately 10,000 km².Physical-chemical parameters, dissolved solids, and seven trace elements were determined in 60 selected water samples. Systematic and accurate measurements of arsenic, flourine, and vanadium were performed for the first time. Three trace element contaminants not reported earlier were found: an important one, selenium, and two others of less known effects, uranium and molybdenum.Eighty-four percent of the water analyzed showed arsenic contents over 0.05 mg/L, maximum contaminant level established by the U.S. Environmental Protection Agency (1982). The frequency distribution of trace elements was analyzed, and its fit to the lognormal distribution was proved by means of the Pearson and Kolmogorov-Smirnov test; the geographic distribution of the seven trace elements was mapped and its correlation with the anion-cation composition of the water was studied.The maximum arsenic, fluorine, vanadium, and uranium contents were found in the western part of the area under study, in waters containing dominant alkali metals in the cation composition. Maximum selenium and antimony contents were found in the eastern part of the area, while molybdenum distribution does not show any relationship with the other two groups. In addition, the geographic distribution of the trace elements seems to be related to the subsurface structure, which has been inferred using interactive digital analysis of Landsat imagery. The movements of the subsoil have disturbed surface and subsurface drainage influencing the water salinity and trace element contents.In order to investigate the origin of the contamination, 54 loess samples were collected in wells at depths ranging from the surface down to the water table. This loess, which has a high proportion of volcanic components, mainly rhyolitic glass, exhibits a chemical composition corresponding to that of a dacite.The loess and the volcanic glass show anomalous contents of all contaminant trace elements, mainly arsenic and selenium. For this reason loess is considered the most important contamination source in the groundwater under study.     

Modes of occurrence of mercury and other trace elements in coals from the warrior field, Black Warrior Basin, Northwestern Alabama

The mineralogic residence and abundance of trace metals is an important environmental issue. Data from the USGS coal quality database show that potentially toxic elements, including Hg, As, Mo, Se, Cu, and Tl are enriched in a subset of coal samples in the Black Warrior Basin of Alabama, USA. Although the coal as-mined typically is low in these elements, localized enrichments occur in high-pyrite coals and near faults. Microscopic analyses demonstrate that the residence of these elements is dominantly in a late-stage pyrite associated with structurally disrupted coal. Further, our data suggest addition of Hg to the coal matrix as well. The source of these trace elements was hydrothermal fluids driven into the Black Warrior Basin by Alleghanian age tectonism.     

A preliminary study on the enrichment mechanism and occurrence of hazardous trace elements in the Tertiary lignite from the Shenbei coalfield, China

The Cr and Ni contents are high in the Eocene lignite of the Shenbei coalfield, which is a small intracontinental basin located in Liaoning Province, China. In this paper, we studied the distribution, origin and occurrence of Cr, Ni and other hazardous trace elements in the Shenbei lignite on the basis of coal petrology, and geochemistry of the lignite and combustion products. The following conclusions on the Shenbei lignite can be drawn: (1) The dominant maceral group in the Shenbei coal is huminite (humodetrinite), accounting for 96%–99% of the total maceral. Inertinite content is less than 1%. Liptinite content (sporinite and cutinite) is 0.2–1.6%. Common minerals in the Shenbei lignite include clay minerals (kaolinite), pyrite and quartz, and calcite and siderite. Chromite is not present in the lignite. (2) Potentially hazardous trace elements such as Co (22 μg/g), Cr (79 μg/g), Cu (63 μg/g), Zn (93 μg/g), V (88 μg/g) and Ni (75 μg/g) are strongly enriched in the Shenbei lignite compared with average concentration of trace elements in the Chinese coal and worldwide lignite. These elements are mainly associated with fulvic acid (FA) and/or coal organic macromolecular compounds in most of the studied lignite samples, indicating an organic association and enrichment of these elements in the Shenbei lignite. (3) Unusually high trace elements contents in the Shenbei lignite are derived mainly from the olivine basalt (country rock of coal basin) that consists of 52.7% plagioclase, 17.8% pyroxene, 14% olivine and 15.5% Ti–Fe oxide minerals. These olivine basalts have higher Cr, Ni, Pb and Zn contents than other types of rock and worldwide basalts do. (4) Fly ash of the Shenbei lignite, with 90% 1–50 μm amorphous particles and 8% 1–10 μm cenosphere, has high contents of Zn (23,707 μg/g), Be (12 μg/g), Sr (1574 μg/g), Pb (486 μg/g) and Cr (349 μg/g). In particular, the ferruginous micro-cenoshperes contain 1–12.79% Zn. Fine bottom ash (<0.031mm) of the Shenbei lignite has higher contents for most of the elements with the exception of Mo, Sn and Zn. Therefore, the potentially environmental and health impact of the fly ash and fine bottom ash should constitute a major concern.     

Concentration and association of minor and trace elements in Mukah coal from Sarawak, Malaysia, with emphasis on the potentially hazardous trace elements

The ash yield and concentrations of twenty-four minor and trace elements, including twelve potentially hazardous trace elements were determined in Mukah coal from Sarawak, Malaysia. Comparisons made to the Clarke values show that Mukah coal is depleted in Ag, Ba, Be, Cd, Co, Mn, Ni, Se, U, and V. On the other hand, it is enriched in As, Cr, Cu, Pb, Sb, Th, and Zn. Among the trace elements studied, V and Ba are associated predominantly with the clay minerals. Manganese, Cr, Cu, Th, and Ni are mostly bound within the aluminosilicate, sulphide and/or carbonate minerals in varying proportions, though a portion of these elements are also organically bound. Arsenic, Pb and Sb are mostly organically bound, though some of these elements are also associated with the sulphide minerals. Zinc is associated with both the organic and inorganic contents of the coal. Among the potentially hazardous trace elements, Be, Cd, Co, Mn, Ni, Se, and U may be of little or no health and environmental concerns, whereas As, Cr, Pb, Sb and Th require further examination for their potential health and environmental concerns. Of particular concern are the elements As, Pb and Sb, which are mostly organically bound and hence cannot be removed by physical cleaning technologies. They escape during coal combustion, either released as vapours to the atmosphere or are adsorbed onto the fine fly ash particles.     

广东省河台含金剪切带中REE及其它微量元素的含量和分布特征

河台含金剪切带中稀土元素(REE)分布特征表明,在剪切过程中REE的活动性与流体/岩石的比例以及流体运移聚集的方式有关。在水/岩比低的深层韧性剪切环境形成的糜棱岩中REE的组成具有继承原岩的特点;在浅层脆性环境以充填方式形成的含金石英脉中REE的含量主要来源于流体;在中浅层过渡环境形成的含金硅质体中REE的分布则受到原岩和流体的共同影响。微量元素的研究证明了河台金矿的形成经历了三个阶段:①韧性阶段。由变质热液沿剪切带的渗滤扩散形成含An小于1×10~(-6)的糜棱岩;②韧-脆性阶段。因剪切带的张开和流体的充填交代在剪切带内产生含An 10×10~(-6)～100×10~(-6)的硅质岩或石英脉;③脆性阶段。受各种张性构造控制在剪切带以内或以外形成含Au 1×10~(-6)～5×10~(-6)的晚期石英脉。     

An attempt to use LA-ICP-SMS to quantify enrichment of trace elements on pyrite surfaces in oxidizing mine tailings

Metals released from oxidation and weathering of sulphide minerals in mine tailings are to a high degree retained at deeper levels within the tailings themselves. To be able to predict what could happen in the future with these secondarily retained metals, it is important to understand the retention mechanisms. In this study an attempt to use laser ablation high-resolution ICP-MS (LA-ICP-SMS) to quantify enrichment of trace elements on pyrite surfaces in mine tailings was performed. Pyrite grains were collected from a profile through the pyrite-rich tailings at the Kristineberg mine in northern Sweden. At each spot hit by the laser, the surface layer was analyzed in the first shot, and a second shot on the same spot gave the chemical composition of the pyrite immediately below. The crater diameter for a laser shot was known, and by estimating the crater depth and total pyrite surface, the total enrichment on pyrite grains was calculated. Results are presented for As, Cd, Co, Cu, Ni and Zn. The results clearly show that there was an enrichment of As, Cd, Cu and Zn on the pyrite surfaces below the oxidation front in the tailings, but not of Co and Ni. Arsenic was also enriched on the pyrite grains that survived in the oxidized zone. Copper has been enriched on pyrite surfaces in unoxidized tailings in the largest amount, followed by Zn and As. However, only 1.4 to 3.1% of the Cd and Zn released by sulphide oxidation in the oxidized zone have been enriched on the pyrite surfaces in the unoxidized tailings, but for As and Cu corresponding figures are about 64 and 43%, respectively. There were many uncertainties in these calculations, and the results shall not be taken too literally but allowed the conclusion that enrichment on pyrite surfaces is an important process for retention of As and Cu below the oxidation front in pyrite rich tailings. Laser ablation is not a surface analysis technique, but more of a thin layer method, and gives no information on the type of processes resulting in enrichment on the pyrite surfaces. Although only pyrite grains that appeared to be fresh and without surface coatings were used in this study, the possibility that a thin layer of Fe-hydroxides occurred must be considered. Both adsorption to the pyrite directly or to Fe-oxyhydroxides may explain the enrichment of As, Cd, Cu and Zn on the pyrite surfaces, and, in the case of Cu, also the replacement of Fe(II) by Cu(II) in pyrite.     

贵州渣拉沟剖面下寒武统黑色硅质岩微量元素富集机制

华南早寒武世发育了一套富有机质黑色硅质岩,其成因尚有较大争议。选择贵州省三都县渣拉沟剖面早寒武世牛蹄塘组底部硅质岩段进行研究,发现该硅质岩具有微量元素富集的特征。其可能的原因包括,静海环境、上升流和热液活动。Ce/Ce*比值显示硅质岩沉积时水体为次氧化条件,不支持静海环境;而Ba、Zn、Cu、Ni、Cd、P与有机碳含量不存在相关关系,也不支持上升流为微量元素富集的主要原因。Al-Fe-Mn三角图、Al2O3/(Fe2O3+Al2O3)、REY配分模式等指标则表明存在热液活动。上述认识与现代上升流、静海环境的微量元素富集系数对比结果相吻合。与华南地区早寒武世初期不同沉积环境硅质岩对比,发现:深海环境并不富集Ba、Zn、Cu、Ni等氧化还原敏感元素,而沿着斜坡相带同沉积断层分布的热液活动,更有可能造成这些微量元素的富集。     

Meteoritic trace elements in lunar rock 14321, 184

The 16 trace elements (Ag, Au, Bi, Br, Cd, Cs, Ge, In, Ir, Rb, Re, Sb, Se, Te, Tl and Zn) were measured by radiochemical neutron activation analysis in six samples of 14321, 184: microbreccia-2 (15), microbreccia-3 (14A, 16A and 19A), basaltic clast (1A), and light matrix material (9A). The 14321 microbreccias typically contain a siderophile-rich ancient meteoritic component, poor in volatiles, which is characterized by low $\text{Ir}\text{Au}$ and $\text{Re}\text{Au}$ ratios (0.25-0.38 and 0.34-0.50, respectively, normalized to Cl). This component also occurs in Apollo 12 KREEP glasses, norite fractions of Apollo 14 1–2 mm soils, Apennine Front breccias, and Cayley Formation material, and may represent ejecta from the Imbrian basin.The basaltic clast 14321, 184-1A closely resembles 14053 in trace element content, and both are 5–10 times higher than mare basalts in volatile trace elements (Br, Cd, Tl). The light matrix material contains 9.2 ± 0.5 per cent of microbreccias, judging from its siderophile content.     

Experimental partitioning of Be,Cs, and other trace elements between cordierite and felsic melt,and the chemical signature of S-type granite

The trace-element signature that cordierite (Crd) imparts to silicic magmas was evaluated by experiment using metapelite mineral mixtures to produce cordierite-bearing peraluminous granitic melts at 200 MPa (P_H2O), from 700 to 850 °C. Most elemental partition coefficients vary with T. Beryllium is strongly compatible, with D_Be^Crd/melt values decreasing linearly from 202.0 to 6.7 as T rises from 700 to 850 °C. Manganese is compatible (D_Mn^Crd/melt=7.67 to 1.92 over the same range of T), and shows similar values to those reported for biotite in silicic melts. Incompatible components include Li, Rb, B, F and P, although Cs is nearly compatible in cordierite, especially at higher T (D_Cs^Crd/melt=~0.19 to 0.60) where the large alkalis are better accommodated structurally. Cordierite appears to be the most effective crystalline reservoir of Be and Cs in metapelites and their anatectic melts. Natural data support the hypothesis that Crd, when present in granitic melts, sequesters Be, Cs and, in the absence of garnet, Mn. S-type granitic rocks containing Crd show consistently low Be contents (mean=0.8 ppm Be with an average range of <1 to 1.20) whereas Crd-free granites (e.g., containing accessory garnet) exhibit distinctly higher Be contents (mean=6 ppm Be with an average range of 3 to 12). These values increase further in evolved facies (mean=69 ppm Be with a an average range of 11 to 145) which commonly give rise to beryl-bearing pegmatites. Whole-rock signatures of Be discriminate source environments of silicic magmas at a resolution equal to the boundaries of the cordierite stability field - e.g., at the P-T-X conditions where cordierite gives rise to garnet+aluminum silicate. Cordierite-bearing granitic rocks contain low Cs contents (mean=1.8 ppm Cs) compared to the Crd-free equivalents (mean=18 ppm Cs). Mn contents also correlate with the presence (mean=0.01 wt% MnO) or absence of Crd (mean=0.09 wt% MnO). Depending on its contribution to anatexis, cordierite may either give or take S-type chemical character from granitic liquids, resulting in a distinctive Crd-associated group of S-type elements. This signature is different from that of micas (high Li, F and, to a lesser degree, Be and Mn). Whole-rock compositions of granites, coupled with notable absences of beryl in their associated pegmatites, indicate that a sizable population of S-type granites originated from Crd-bearing sources. The normative Crd component of silicic peraluminous melts is Д wt% to 850 °C. Higher modal contents of cordierite reflect either restite entrainment or peritectic reactions which produce Crd after magma ascent to shallow depths. The distinctive trace-element signature of cordierite now provides improved resolution of the source mineralogy for S-type magmas.