Trace elements in the Goze Delchev coal deposit, Bulgaria

The geochemistry of trace elements in the underground and open-pit mine of the Goze Delchev subbituminous coal deposit have been studied. The coals in both mines are highly enriched in W, Ge and Be, and at less extent in As, Mn and Y as compared with the world-wide Clarkes for subbituminous coals. Ni and Ti are also enhanced in the underground coals, and Zr, Cr and Mo in the open-pit mine coals.Characteristic for the trace element contents in the deposit is a regular variation with depth. The following patterns were distinguished for profile I: a — the element content decreases from the bottom to the top of the bed paralleling ash distribution (Fe, Co, As, Sb, V, Y, Mo, Cs, REE, Hf, Ta, Th, P and Au); b — Ge and W are enriched in the near-bottom and near-top coals; c — in the middle part of the bed the content of K and Rb is maximal, while that of U is slightly enriched; d — Ba content decreases from the top to the bottom of the bed. In profile II, W and Be contents decrease from the bottom to the top. The near-bottom, and especially the near-roof samples of profile IV are highly enriched in Ge, while for W the highest is the content of the near-bottom sample.Ge, Be, As, Mn, Cl and Br are mainly organically associated. The organic affiliation is still strong for Co, B, Sr, Ba, Sb, U, Th, Mo, La, Ce, Sm, Tb and Yb in the underground coals, and Fe, Co, Na, W, Sr, Y and Ag in the coals from the open-pit mine. K, Rb, Ti, Zr, Hf and Ta are of dominant inorganic affinity. The chalcophile and siderophile elements correlate positively with Fe and each other and may be bound partly with pyrite or other sulphides and iron containing minerals.Compared statistically by the t-criteria, the elements Na, Li, Cu, Zn, Pb, Cr, Ni, Co, Mo, Fe and Be are of higher content in the open-pit mine. Tungsten is the only element of higher concentration in the underground mine. The contents of Ge, As, Sr, V, Mn, Y, Zr and P are not statistically different in both mines.It was supposed that there were multiple sources of the trace elements in the deposit. The source of the highly enriched elements (W, Ge, Be, and As) most probably were the thermal waters in the source area. The contemporary mineral springs are of high content of these elements. Another source were the hosting Mesta volcanic rocks, which are enriched in Sb, Mo, Hf, U, Th, As, Li and Rb. Some of the volcanics were hydrothermally altered and enriched or depleted of many elements. Thus, the hydrothermal solutions were also suppliers of elements for the coals. It is obvious that the contents, distribution and paragenesis, of the trace elements in both Goze Delchev coals reflect the geochemical specialization of the source area, including rocks, paleo- and contemporary thermal waters.     

Differences in trace metal concentrations among fluvial morphologic units and implications for sampling

 This study examines the segregation of trace metals within and between fluvial morphologic units in sand-sized and finer bed sediments in a cobble bed stream. The types of fluvial morphologic units sampled are low gradient riffles, high gradient riffles, glides, eddy drop zones, lateral scour pools, attached bars, and detached bars. Three to nine samples were collected from ten of each type of morphologic unit. All 12 metals show significantly different concentrations between some morphologic units in sediments smaller than 2 mm. Eddy drop zones and attached bars consistently have the highest metal concentrations, while low gradient riffles, high gradient riffles, and glides typically have the lowest concentrations. Metals showing the greatest between-unit variability are Al, Cr, Fe, Cu, and Ti, followed by Co, Mn, and Pb, while Mg, Mn, V, and Zn display relatively few differences between units. Lateral and longitudinal variations of metals within units are not significant, and there was no consistent, predictable variation in metal concentrations with distance downstream. Results indicate that metal studies in other gravel- and cobble-bed streams should include a reconnaissance survey to determine variations between morphologic units, stratify sampling by morphologic unit, and analyze spatial autocorrelation to determine sample spacing. Received: October 1997 · Accepted: 23 March 1998     

Mobility of Al, Co, Cr, Cu, Fe, Mn, Ni and V in sulphide-bearing fine-grained sediments exposed to atmospheric O2: an experimental study

 The major aim was to increase our knowledge on the behaviour of Al, Co, Cr, Cu, Fe, Mn, Ni and V in sulphide-bearing fine-grained sediments exposed to atmospheric oxygen. Samples of this type of sediment collected in a previous investigation at eight sites in western Finland were digested in HClO₄-HNO₃-HCl-HF at 200  °C and in HCl:HNO₃:H₂O at 95  °C (aqua regia), and subjected to extractions with ammonium acetate and hydrogen peroxide. Metals and S in the leachates were determined with ICP-AES. The results of the chemical analyses are compared with previously reported experimental data. The concentrations of Al and Fe in the sulphide-bearing fine-grained sediments are about 7% and 5%, respectively. Of the trace metals studied, Mn is most abundant followed in decreasing order by V>Cr>Ni>Cu>Co. On oxidation of the sediments, high proportions of Co, Mn and Ni, intermediate proportions of Cu but low proportions of Fe, Al, Cr and V are released. The extent of the release of a metal on oxidation is controlled either by (1) the level to which the pH of the sediments drops on oxidation (Al, Cu, Cr, V), (2) the amount of the metal associated with easily reduced phases (metal sulphides) in the sediments (Ni, Co) or (3) the sum of the amount associated with reduced phases and adsorbed on soil compounds (Mn). No control of the release of Fe on oxidation of the sediments was identified. Based on the results of the study it is argued that artificial drainage and the subsequent oxidation of sulphide-bearing sediments will result in extensive leaching of Co, Mn and Ni, moderate leaching of Cu and limited leaching of Cr and V into drainages. The major elements, Fe and Al, have the potential to be mobilised and leached in large amounts, though the proportions mobilised/leached will remain low. It is suggested that the identification of sulphide-bearing sediments with a high potential of metal release should be based on determination of metals in easily mobilised reduced compounds (dissolved e.g. in H₂O₂) and of the level to which the pH of the sediments drops on oxidation. Received: 16 October 1997 · Accepted: 9 March 1998     

Geological factors influencing the concentration of trace elements in the Philippi peatland, eastern Macedonia, Greece

Six peat samples obtained from the Holocene and the Weichselian of the Philippi peat deposit, eastern Macedonia, Greece, were analyzed for 48 trace elements by Inductively Coupled Plasma–Mass Spectrometry (ICP–MS). The ash contents of these samples were also determined. Most of the trace elements are associated with the minerals in the peat, while Ge, Mo, Pb, Se, Ta, Tl, U, and W display a greater affinity with the organic matter. Compared with crustal averages (Clarke concentrations), the Philippi peat is enriched in some elements (Ag, As, Au, Cd, Mo, Se, Te, U, and W) because of the respective mineralizations in the area. The Philippi peat is also enriched in Cr, Cu, Mo, Pb, Sc, Sn, T, V, Y, and Zn in comparison with typical fen peats, as well as in As, Cr, Mo, Se, and U in comparison with typical coals. Climatic and hydrogeological conditions strongly influenced the peat-forming environment resulting in a differentiation between Holocene and Weichselian peat. Generally, the Holocene peat contains lower concentrations of trace elements in the northern and southern part of the fen, than the Weichselian one. The opposite trend is observed in the fen area close to the western basin margins.     

吉林省西南部地区花岗岩类微量元素特征研究及成因探讨

本文对吉林省西南部地区花岗岩类的微量元素特征进行了系统的研究,并利用微量元素的某些特征值对区内花岗岩成因进行了探讨。     

Sources and sinks of atmospheric methane

In 1972 average mixing ratio of methane in the troposphere was 1.41 ppm and 1.3 ppmv for the northern and southern hemisphere, respectively, which corresponds to a total amount of 4×10¹⁵ g of CH₄ present in the atmosphere. Most is of recent biologic origin.¹⁴C analyses show that no more than 20 percent is released by fossil sources. The various ecosystems producing CH₄ are discussed and the total annual production is estimated to lie between 5.5×10¹⁴ g/yr and 11×10¹⁴ g/yr. The corresponding turnover times for atmospheric CH₄ range from 4 to 7 yrs. The destruction of CH₄ takes place mainly in the troposphere, most probably through the reaction of CH₄ + OH CH₃ + H₂O. About 10 percent of the CH₄ is destroyed in the stratosphere. The CH₄ cycle contributes on the order of 1 percent to the atmospheric carbon cycle.     

A two-dimensional photochemical model of the stratosphere with Rayleigh scattering

Computations of concentrations of minor stratospheric gases using a two-dimensional model of the stratosphere are reported. The model includes Rayleigh scattering. This results in an increase in the photodissociation rate computation time by a factor of 1.5. The effect of ground albedo is assessed by comparing our results with a calculation of photolysis rates for a constant albedo with latitude. Comparison of results with a reference model including only molecular absorption are also made. The largest differences (50%) occur in NO and OH. An approximate expression for including the effects of Rayleigh scattering and surface reflectance in multi-dimensional models is suggested.     

The ocean as source or sink of reactive trace-gases

Summary After a brief review on recent experimental work on the uptake resp release of SO₂ and NH₃ by the ocean, new results on the distribution of these reactive trace-gases in the marine atmosphere are presented. In the case of SO₂ there is no doubt that the ocean acts as a sink. In the case of NH₃ new observations and calculations show that under certain conditions the ocean may be a NH₃ source.     

Further discussion on the intercomparison of the trace metal concentrations and particle size of fluvial sediment recovered from two centrifuge systems

A single large volume water sample taken at the mouth of the Upper Rhone River on Lake Geneva was processed directly in parallel through two continuous flow centrifuges, a Westphalia and an Alfa-Laval. Sediment was recovered from the Westphalia, and separately from the bowl and brass core of the Alfa-Laval. The three sediment samples were analyzed for particle size and the following elements: Zn, Cu, Mn, Cr, P, Co, B, V, Be, Sr, Na, Pb, Ni, Ba, Fe, Ca, and Mg. Results indicate that the particle size recovery of both machines is similar when sediment from the brass core and bowl of the Alfa-Laval are combined, and that the recovery for all elements other than Cu, V, B, and Pb are the same when the particle size differences are taken into account. Sediment from the Alfa-Laval brass core is clearly contaminated by Cu, B and is also elevated in V and Pb but not to a significant extent. The sediment recovered from the bowl of the Alfa-Laval is contaminated only with Cu, with a 10 ppm increase over the 52 ppm recovered in the Westphalia sediment. Operating procedures involve the discarding of the brass core sediment and the mixing of the Alfa-Laval bowl sediment with that from the Westphalia. The consequent increase in Cu is estimated at less than 5 ppm or within the confidence level of the analysis. These procedures are recommended to all operators of non modified Alfa-Laval units.     

Multiple controls on the paleoenvironment of the Early Cambrian marine black shales in the Sichuan Basin,SW China: Geochemical and organic carbon isotopic evidence

In order to understand the paleoenvironment of the Early Cambrian black shale deposition in the western part of the Yangtze Block, geochemical and organic carbon isotopic studies have been performed on two wells that have drilled through the Qiongzhusi Formation in the central and southeastern parts of Sichuan Basin. It shows that the lowest part of the Qiongzhusi Formation has high TOC abundance, while the middle and upper parts display relative low TOC content. Redox-sensitive element (Mo) and trace elemental redox indices (e.g., Ni/Co, V/Cr, U/Th and V/(V + Ni)) suggest that the high-TOC layers were deposited under anoxic conditions, whereas the low-TOC layers under relatively dysoxic/oxic conditions. The relationship of the enrichment factors of Mo and U further shows a transition from suboxic low-TOC layers to euxinic high-TOC layers. On the basis of the Mo-TOC relationship, the Qiongzhusi Formation black shales were deposited in a basin under moderately restricted conditions. Organic carbon isotopes display temporal variations in the Qiongzhusi Formation, with a positive excursion of δ¹³C_org values in the lower part and a continuous positive shift in the middle and upper parts. All these geochemical and isotopic criteria indicate a paleoenvironmental change from bottom anoxic to middle and upper dysoxic/oxic conditions for the Qiongzhusi Formation black shales. The correlation of organic carbon isotopic data for the Lower Cambrian black shales in different regions of the Yangtze Block shows consistent positive excursion of δ¹³C_org values in the lower part for each section. This excursion can be ascribed to the widespread Early Cambrian transgression in the Yangtze Block, under which black shales were deposited.