Analysis of arsenic speciation in mine contaminated lacustrine sediment using selective sequential extraction,HR-ICPMS and TEM

In order to determine how As speciation in lacustrine sediment changes as a function of local conditions, sediment cores were taken from three lakes with differing hydrologic regimes and subjected to extensive chemical and TEM analysis. The lakes (Killarney, Thompson and Swan Lakes) are located within the Coeur d’ Alene River system (northern Idaho, USA), which has been contaminated with trace metals and As, from over 100 a of sulfide mining. Previous analyses of these lakebed sediments have shown an extensive amount of contaminant metals and As associated with sub-μm grains, making them extremely difficult to analyze using standard methods (scanning electron microscopy, X-ray diffraction). Transmission electron microscopy offers great advantages in spatial resolution and can be invaluable in determining As speciation when combined with other techniques. Data indicate that because of differences in local redox conditions, As speciation and stability is dramatically different in these lakes. Killarney and Thompson Lakes experience seasonal water-level fluctuations due to drawdown on a downstream dam, causing changes in O₂ content in sediment exposed during drawdown. Swan Lake has relatively constant water levels as its only inlet is dammed. Consequently, Killarney and Thompson Lakes show an increase in labile As-bearing phases with depth, while Swan Lake data indicate stable As hosts throughout the sediment profile. Based on these observations it can be stated that As in lakebed sediments is much less mobile, and therefore less bioavailable, when water is kept at a constant level.     

A comparison between heavy metals released from soil and its efficient speciation extracted by sequential extraction procedure

A simulating experiment was carried out on the interaction between natural precipitation and soil. The results demonstrated that the contents of heavy metals （V, Co, Cr, and Ni） released from soil into the solution under Earth＇s surface conditions are higher than the contents of those metals bonded to exchangeable species, which were extracted by sequential extraction procedure recommended by Tessier and others in 1979. It is demonstrated that the metals bonded to other 3 species （carbonate, Fe-Mn oxide, and organic matter） except those bonded to the exchangeable species in efficient speciation can be released under the Earth＇s surface conditions, when pH=4 in the reaction system, and the higher correlation coefficient indicated that the concentrations of heavy metals released from soil into the solution vary approximately with reaction time in terms of index regulations.     

土壤和沉积物中元素的化学形态及其顺序提取法

介绍了形态分析的概念和化学形态分析方法,探讨了广泛应用于土壤、沉积物重金属形态分析中的Tessier和BCR顺序提取方案及其异同,综述了顺序提取方法在地球化学、环境科学、农业科学等方面的应用及中国相关标准物质的研制现状。     

Accelerated aqueous leaching of selenium and arsenic from coal associated rock samples with selenium speciation using ultrasound extraction

Ultrasound extraction was used to compare the accelerated release rates of selenium and arsenic from three rocks (BT700, BT 571 and BT 60) that are associated with mountaintop mining and valley fill coal mining practiced in southern parts of West Virginia, USA. The concentrations of arsenic released from rocks were found to be three orders of magnitude higher than that of selenium. The accelerated leaching rate constants were ten times higher for arsenic compared to selenium. Se (IV) was found to be stable under ultrasound extraction conditions used whereas As (III) was quickly oxidized to As (V). BT700 was found to have more Se (IV) compared to BT571 while BT60 did not have any significant Se (IV) concentrations. Such compositional and kinetic information becomes important when determining suitable mining waste treatment protocols that have to be undertaken to different types of overburden before it is dumped in valleys.     

Element fractionation by sequential extraction in a soil with high carbonate content

The influence of carbonate and other buffering substances in soils on the results of a 3-step sequential extraction procedure (BCR) used for metal fractionation was investigated. Deviating from the original extraction scheme, where the extracts are analysed only for a limited number of metals, almost all elements in the soils were quantified by X-ray fluorescence spectroscopy, in the initial samples as well as in the residues of all extraction steps. Additionally, the mineral contents were determined by X-ray diffractometry. Using this methodology, it was possible to correlate changes in soil composition caused by the extraction procedure with the release of elements. Furthermore, the pH values of all extracts were monitored, and certain extraction steps were repeated until no significant pH-rise occurred. A soil with high dolomite content (27%) and a carbonate free soil were extracted. Applying the original BCR-sequence to the calcareous soil, carbonate was found in the residues of the first two steps and extract pH-values rose by around two units in the first and second step, caused mainly by carbonate dissolution. This led to wrong assignment of the carbonate elements Ca, Mg, Sr, Ba, and also to decreased desorption and increased re-adsorption of ions in those steps. After repetition of the acetic acid step until extract pH remained low, the carbonate was completely destroyed and the distributions of the elements Ca, Mg, Sr, Ba as well as those of Co, Ni, Cu, Zn and Pb were found to be quite different to those determined in the original extraction. Furthermore, it could be shown that the effectiveness of the reduction process in step two was reduced by increasing pH: Fe oxides were not significantly attacked by the repeated acetic acid treatments, but a 10-fold amount of Fe was mobilized by hydroxylamine hydrochloride after complete carbonate destruction. On the other hand, only small amounts of Fe were released anyway. Even repeated reduction steps did not destroy the amorphous Fe oxides completely, showing that 0.1 mol L⁻¹ hydroxylamine hydrochloride was not strong enough to attack these oxides effectively.The extraction sequences were carried out not only on the soil samples, but also on their coarse and fine fractions (> or <2 μm). The fine fraction of the calcareous soil contained only 10% dolomite, but was enriched in organic matter and clay minerals, which also resulted in increased extract pH-values during the sequential extraction. Hence, the effects on ion release in the fine fraction were similar to those of the whole soil. Since the destruction of the organic matter was incomplete after regular oxidation, the H₂O₂-treatment of the fine fraction had to be repeated. The addition of the extractable amounts of the two fractions showed good agreement to the results obtained for extraction of the whole soils. Likewise the pH-values of the carbonate-free soil extracts did not increase significantly, therefore it was concluded that repetitions of extraction steps for this soil were not necessary.Extract-pHs should always be controlled so that extraction conditions are comparable; to be able to use the BCR extraction scheme or similar ones for carbonate- and organic-rich samples this is mandatory. Single extraction steps should be repeated if pH rises too much; additionally the oxidizing step should be performed more than twice for samples rich in organic substances, depending upon the violence of the reaction with H₂O₂. If these precautions are neglected the validity of the extraction data is likely to be questionable.     

Mercury speciation in tailings of the Idrija mercury mine

Five hundred years of mercury (Hg) mining activity in Idrija, Slovenia caused widespread Hg contamination. Besides Hg emissions from the ore smelter, tailings have been found to be the major source of river sediment contamination. In the present study, solid phase binding forms and the aqueous mobility of Hg have been investigated in tailings of the Idrija Hg mine by means of a pyrolysis technique and aqueous Hg speciation. Results show that Hg binding forms differ with the age of the tailings due to the processing of different ores with different roasting techniques. In older tailings, the predominant Hg species is cinnabar (HgS), due to incomplete roasting, whereas in tailings of the 20th century the amount of cinnabar in the material decreased due to a higher efficiency of the roasting process and the increasing use of ores bearing native Hg. In younger tailings, metallic Hg (Hg⁰) sorbed to mineral matrix components such as dolomite and Fe-oxyhydroxides became the predominant Hg binding form in addition to unbound Hg⁰ and traces of HgO. Leaching tests show that in younger tailings high amounts of soluble Hg exist in reactive form. In older tailings most of the soluble Hg occurs bound to soluble complexes. It might be assumed that in the long term, matrix-bound Hg⁰ could be bound to humic acids derived from soils covering the tailings. This means that, despite the lower total Hg concentrations found in the younger tailings, the long-term risk potential of its mobile matrix-bound Hg⁰ is higher than that of older tailings bearing mostly immobile cinnabar.     

Mercury speciation and distribution in Aha Reservoir which was contaminated by coal mining activities in Guiyang, Guizhou, China

Two sampling campaigns were carried out in March and August 2005 representing dry and wet seasons, respectively, to investigate the distribution patterns of Hg species in the water column and sediment profiles at two sampling stations in Aha Reservoir located in Guiyang, Southwestern China. Aha Reservoir has been contaminated by Hg due to small scale coal mining activities. Mercury concentrations in both water and sediment were elevated. A clearly seasonal variation of dissolved Hg (DHg), particulate Hg (PHg) and total Hg (THg) concentrations in the water column was observed. The concentrations of these Hg species in the wet season were significantly higher than in the dry season. Runoff input and diffusion of Hg from sediments could be the reasons for elevated concentrations of these Hg species in the wet season. The contaminated sediment is acting as a secondary contamination source for both inorganic Hg (IHg) and methylmercury (MeHg) to the overlying water. The cycling of Mn in the sediment governs the diffusion process of IHg to the water column. In the dry season (winter and spring), Mn occurs as MnO₂ because the uppermost part of sediment is in an oxic condition and Hg ions are absorbed by MnO₂. In the wet season (summer and fall), the uppermost part of the sediment profile is in a reduced condition because of stratification of the water column and MnO₂ is reduced to Mn²⁺, which results in transformation of Hg²⁺ into porewater as Mn²⁺ became soluble. This causes a higher diffusive flux of IHg from sediment to overlying water in the wet season. Both sampling stations showed a consistent trend that THg concentrations decreased in the uppermost part of sediment cores. This demonstrated that the measures taken to reduce ADM contamination to Aha Reservoir also reduced Hg input to the reservoir. Methyl Hg diffusive fluxes from sediment to overlying water were higher in the wet season than the dry season demonstrating that high temperatures favor Hg methylation processes in sediment.     

Evaluation of uranium and arsenic retention by soil from a low level radioactive waste management site using sequential extraction

The European Communities Bureau of Reference (BCR) and Chunguo sequential extraction procedures were employed to evaluate the retention of U and As by a soil contaminated with low level radioactive waste. Modifications were made to both procedures to optimize the measurement of soil and extractant samples using epithermal neutron activation analysis. Based on the BCR procedure, approximately 20% of the U appeared to be bound to the carbonate fraction, 10% to the mineral oxide fraction and 20% to the organic fraction. In the case of As, the majority was strongly bound in the residue fraction. The results obtained with the Chunguo procedure supported these conclusions to some extent, in that the majority of the U and As was found to be strongly bound to the soil in a manner consistent with its presence in the residue fraction.     

煤矸石堆周围土壤重金属污染特征分析--以焦作市中马村矿为例

利用扇形布点法采集了焦作市中马村矿矸石堆周围土壤，对其中的Cr、Pb、Cu、Mn4种重金属含量进行了研究。结果表明：煤矸石的堆放对周围土壤造成不同程度的污染，重金属的含量随离矸石堆距离增大呈减小的趋势，主要受到风向的影响。     

Metal speciation in coastal marine sediments from Singapore using a modified BCR-sequential extraction procedure

The chemical speciation of heavy metals (Cd, Cr, Cu, Ni, Pb and Zn) in marine sediments from two coastal regions of Singapore (Kranji in the NW, and Pulau Tekong in the NE) was determined using the latest version of the 3-step sequential extraction procedure, as described by the European Community Bureau of Reference (1999). To obtain a mass balance, a fourth step, i.e., digestion and analysis of the residue was undertaken using a microwave-assisted acid digestion procedure. The total content of all metals except for Pb in sediments was greater in Kranji than in Pulau Tekong. All metals, except Cd were more mobile and bio-available in Kranji, where metals were present at higher percentages in the acid-soluble fractions (the most labile fraction). In sediments from Kranji, the mobility order of the heavy metals studied was Cd > Ni > Zn > Cu > Pb > Cr, whereas sediments from Pulau Tekong showed the same order for Cd, Ni, Pb and Cr, but had a reverse order for Cu and Zn (Cu > Zn). The highest percentages of Cr, Ni and Pb were found in the residual fractions in both Kranji (78.9%, 54.7%, 55.9%, respectively) and Pulau Tekong (82.8%, 77.3%, 62.2%, respectively), meaning that these metals were strongly bound to the sediments. Results are consistent with findings from Barcelona, Spain where similar results for Cr and Ni have also been reported for marine sediments. The sum of the 4 steps (acid-soluble + reducible + oxidizable + residual) was in good agreement with the total content, which implies that the accuracy of the microwave extraction procedure in conjunction with the GFAAS analytical method is assured.     

Hydrogeologic factors affecting gas content distribution in coal beds

Gas content in coal is not fixed but changes when equilibrium conditions within the reservoir are disrupted. Therefore, gas content distribution in coal varies laterally within individual coal beds, vertically among coal beds in a single well, and within thicker coal beds. Major hydrogeologic factors affecting gas content variability include gas generation, coal properties, and reservoir conditions. Gas generation affects gas content variability on a regional scale, whereas coal properties influence gas content distribution on a regional and local scale. Reservoir conditions affect gas content more locally within specific fields or individual wells. The potential for high gas content is controlled directly by the amount of thermogenic and secondary biogenic gases generated from the coal which in turn are controlled by burial history, maceral composition, and basin hydrodynamics. Variability in mineral matter (ash) and moisture content, sorption behavior among macerals, diffusion coefficients, and permeability result in heterogeneous gas content distribution. Gas content decreases with decreasing pressure and temperature, and coal beds become undersaturated with respect to methane during basin uplift and cooling. Gas content generally increases where conventional and hydrodynamic trapping of coal gases occur and may decrease in areas of active recharge with downward flow potential and/or convergent flow where there is no mechanism for entrapment.     

Notes on the marginal enrichment of Germanium in coal beds

Germanium distribution in coal has long been a topic of interest. The enrichment of Ge near margins of coals, including the margins of partings within the coal, has been noted in many coals from numerous coalfields throughout the world. In this paper, a summary of literature on Ge geochemistry on the upper and lower margins of coal seams, with special emphasis on the literature of Russia, and the former Soviet Union, and Japan, is presented.     

电感耦合等离子体质谱法测定砂岩型铀矿样品中分步提取的铀

本文研究地质样品中铀形态的分析方法及应用技术,以进一步说明铀形态分析在地球化学找矿中的重要作用。该方法参考Tessier流程,将样品中的铀分为可交换离子态、碳酸盐结合态、铁锰氧化物结合态、硫化物及有机物结合态和结晶态,分别提取,提取溶液用高分辨率电感耦合等离子体质谱仪进行测量。设计的形态提取配方具有良好的可选择性和可重复性,经过国家标准物质、国际形态标准物质和人工模拟样品验证,证明形态提取试剂配方适合所定义的形态分析。通过对实际样品(总量铀为635μg/g)验证表明,碳酸盐结合态铀提取结果的可重复性最好(RSD为2.6%),其次为硫化物及有机物结合态铀(RSD为4.0%)、结晶态铀(RSD为6.0%)和铁锰氧化物结合态铀(RSD为6.1%),可交换离子态铀提取结果的可重复性最差(RSD为26%)。碳酸盐结合态铀与结晶态铀之比,可以用于反映地下铀矿的存在概率。     

Delineation of the distinctive nature of tertiary coal beds

Floral character in mires has changed progressively through time. In the Carboniferous, pteridophytes, sphenophytes and lycophytes were dominant but by the Permian gymnosperms were an important component of mire flora. During the early Mesozoic gymnosperms remained the characteristic mire vegetation, together with pteridophytes, and conifers became dominant during the Jurassic. Cretaceous and Paleocene vegetation are similar, with taxodiaceous flora being important in mire vegetation. From the Eocene onwards, however, angiosperms were increasingly dominant in mire communities and in the Miocene herbaceous vegetation began to play a significant role. Together with these changes in floral character at least three aspects of coal character also appear to vary sequentially with time and are distinctive in the Tertiary: (1) proportions and thickness of vitrain banding, (2) coal bed thickness and (3) proportions of carbonised material. A compilation has been made of data from the coal literature comparing older coals with those of the Tertiary, in order to give a perspective in which to examine Tertiary coals. It was found that only Tertiary coals contain significant proportions of coal devoid of vitrain bands. In addition, Tertiary coals are the thickest recorded coal beds and generally contain low percentages of carbonised material (many less than 5%) as compared to older coals. It is interesting to note that Paleocene coal beds are similar to Cretaceous coals in that they tend to be thinner and contain higher proportions of carbonised material than do younger Tertiary coals.The absence of vitrain bands in some Tertiary coal beds is thought to result from the floras dominated by angiosperms, which are relatively easily degraded as compared to gymnosperms. The thickness of Tertiary coals may be related to an increase in biomass production from the Carboniferous through to the Tertiary, as plants made less investment in producing lignin, an energy-intensive process. In addition, with less lignin in plants, easier degradation of biomass may have facilitated nutrient recycling which, in turn, led to greater biomass production. Increased biomass production may have also ‘diluted’ the carbonised material present in some Tertiary peats, leading to lower proportions in the coal. Another possible cause of decreased carbonised components in Tertiary coal is that decreasing lignin content resulted in decreased charring during fires, as lignin is particularly prone to charring. A third possibility is that the carbonised component of peat may be concentrated during coalification so that Tertiary coals, generally of lower rank than Mesozoic or Paleozoic coals, contain a smaller fraction of carbonised plant material. It is not at present clear which of these mechanisms may have affected carbonised material in peat and coal but it is clear that lignin type and content has had an important role in determining peat and coal character since the Paleozoic.     

The determination of minor and trace element associations in coal using a sequential microwave digestion procedure

A sequential extraction procedure, using acid digestion in a CEM MDS-81D® microwave system, is reported for the investigation of trace and minor element associations in coal in (1) mineral phases other than pyrite, (2) pyrite and (3) the organic matrix. The concentrations of sulphate, pyrite and organic sulphur can also be determined by this method. The extract solutions from each stage are rapidly analysed by ICP-AES. The association of major, minor and trace elements with mineral and organic phases is suggested for a suite of certified reference coal samples. In stage 1, a significant percentage of the total Ba, Co, Cr, Cu, Mn, Ni, Pb and Sr was extracted suggesting an association with silicate, carbonate, sulphate and phosphate minerals for these elements. In stage 2, a proportion of the Cu, Mn, Ni, Pb and Zn was dissolved implying the occurrence of these elements in pyrite. An association with the organic matrix is suggested for Cr and also for Ba and Sr in lower rank coals.     

Palynology of late Middle Pennsylvanian coal beds in the Appalachian Basin

Fossil spores and pollen have long been recognized as valuable tools for identifying and correlating coal beds. This paper describes the palynology of late Middle Pennsylvanian coal beds in the Appalachian Basin with emphasis on forms that assist both intra- and interbasinal coal bed correlation.Stratigraphically important palynomorphs that originate in late Middle Pennsylvanian strata include Torispora securis, Murospora kosankei, Triquitrites minutus, Cadiospora magna, Mooreisporites inusitatus, and Schopfites dimorphus. Taxa that terminate in the late Middle Pennsylvanian include Radiizonates difformis, Densosporites annulatus, Dictyotriletes bireticulatus, Vestispora magna, and Savitrisporites nux. Species of Lycospora, Cirratriradites, Vestispora, and Thymospora, as well as Granasporites medius, Triquitrites sculptilis, and T. securis end their respective ranges slightly higher, in earliest Late Pennsylvanian age strata.Late Middle Pennsylvanian and earliest Late Pennsylvanian strata in the Appalachian Basin correlate with the Radiizonates difformis (RD), Mooreisporites inusitatus (MI), Schopfites colchesterensis–S. dimorphus (CP), and Lycospora granulata–Granasporites medius (GM) spore assemblage zones of the Eastern Interior, or Illinois Basin. In the Western Interior Basin, these strata correlate with the middle-upper portion of the Torispora securis–Laevigatosporites globosus (SG) and lower half of the Thymospora pseudothiessenii–Schopfites dimorphus (PD) assemblage zones. In western Europe, late Middle Pennsylvanian and earliest Late Pennsylvanian strata correlate with the middle-upper portion of the Torispora securis–T. laevigata (SL) and the middle part of the Thymospora obscura–T. thiessenii (OT) spore assemblage zones. Allegheny Formation coal beds also correlate with the Torispora securis (X) and Thymospora obscura (XI) spore assemblages, which were developed for coal beds in Great Britain.     

Catchment scale geostatistical simulation and uncertainty of soil erodibility using sequential Gaussian simulation

Soil erodibility (K) affects sediment delivery to streams and needs to be appropriately quantified and interpolated as a fundamental geographic variable for implementing suitable catchment management and conservation practices. The spatial distribution of K for erosion modelling at non-sampling grid locations has traditionally been estimated using interpolation algorithms such as kriging which do not adequately represent the uncertainty of estimates. These methods cause smoothing effects through overestimating the low values and underestimating the large values. In this study observed values were used to implement a sequential Gaussian simulation (SGS) procedure to evaluate the certainty of modelled data. Soil erodibility values were computed using 41 soil samples taken from the top 10 cm soil layer regularly distributed across four catchments, 367–770 ha in area, within Kangaroo River State forest, New South Wales (NSW). One hundred realisations were applied in the simulation process to provide spatial uncertainty and error estimates of soil erodibility. The results indicated that values simulated by the SGS algorithm produced similar K values for the neighbouring cells. At the pixel level, the SGS approach generated a reliable estimation of soil erodibility in most areas. Spatial variation of the K factor in this study was strongly related to soil landscape differences across the catchments; within catchments slope gradient did not have a substantial impact on the numerical values of the K factor using pixel-by-pixel comparisons of raster grid maps.     

Mercury in coal and the impact of coal quality on mercury emissions from combustion systems

The proportion of Hg in coal feedstock that is emitted by stack gases of utility power stations is a complex function of coal chemistry and properties, combustion conditions, and the positioning and type of air pollution control devices employed. Mercury in bituminous coal is found primarily within Fe-sulfides, whereas lower rank coal tends to have a greater proportion of organic-bound Hg. Preparation of bituminous coal to reduce S generally reduces input Hg relative to in-ground concentrations, but the amount of this reduction varies according to the fraction of Hg in sulfides and the efficiency of sulfide removal. The mode of occurrence of Hg in coal does not directly affect the speciation of Hg in the combustion flue gas. However, other constituents in the coal, notably Cl and S, and the combustion characteristics of the coal, influence the species of Hg that are formed in the flue gas and enter air pollution control devices. The formation of gaseous oxidized Hg or particulate-bound Hg occurs post-combustion; these forms of Hg can be in part captured in the air pollution control devices that exist on coal-fired boilers, without modification. For a given coal type, the capture efficiency of Hg by pollution control systems varies according to type of device and the conditions of its deployment. For bituminous coal, on average, more than 60% of Hg in flue gas is captured by fabric filter (FF) and flue-gas desulfurization (FGD) systems. Key variables affecting performance for Hg control include Cl and S content of the coal, the positioning (hot side vs. cold side) of the system, and the amount of unburned C in coal ash. Knowledge of coal quality parameters and their effect on the performance of air pollution control devices allows optimization of Hg capture co-benefit.