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.     

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.     

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。     

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.     

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.     

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.     

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。     

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.     

Abundance of sulfur in Eocene coal beds from Bapung, Northeast India

At 625°C the percentage of sulfur in the non-volatile portion of the Bapung coal beds ranges from 1.08 to 3.10 wt.%, with the pyritic sulfur ranging from 0.02 to 0.32 wt.%, the sulfate sulfur ranges from 0.02 to 0.30 wt.%, and the organic sulfur from 0.88 to 2.49 wt.%. The total sulfur in the Bapung coal ranges from 2.50 to 12.44%. Organic sulfur appears to be more abundant among the different sulfur species. However, the pyritic sulfur increases quickly as the total sulfur content increases at 925°C, the percentage of sulfur in non-volatile portion ranges from 1.27 to 2.54 wt.%, with pyritic sulfur ranging from 0.02 to 0.56 wt.%, sulfate sulfur ranges from 0.04 to 0.16 wt.%, and the organic sulfur from 1.15 to 2.03 wt.%.     

Mercury mobility and bioavailability in soil from contaminated area

The mobility and bioavailability of mercury in the soil from the area near a plant using elemental mercury for manufacturing thermometers, areometers, glass energy switches and other articles made of technical glass has been evaluated. Mercury has been determined by sequential extraction method and with additional thermo desorption stage to determine elemental mercury. The procedure of sequential extraction involves five subsequent stages performed with the solutions of chloroform, deionized water, 0.5 M HCl, 0.2 M NaOH and aqua regia. The mean concentration of total mercury in soil was 147 ± 107 μg g⁻¹ dry mass (range 62–393), and the fractionation revealed that mercury was mainly bound to sulfides 56 ± 8% (range 45–66), one of the most biounavailable and immobile species of mercury in the environment. The fractions that brought lower contribution to the total mercury content were semi-mobile humic matter 22 ± 9% (range 11–34) and elemental mercury 17 ± 5% (range 8–23). The contributions brought by the highly mobile and toxic organomercury compounds were still lower 2.3 ± 2.7% (range 0.01–6.5). The lowest contributions brought the acid-soluble mercury 1.5 ± 1.3% (range 0.1–3.5) and water-soluble mercury 1.0 ± 0.3% (range 0.6–1.7). The surface layer of soil (0–20 cm) was characterized by higher mercury concentrations than that of the subsurface soil (60–80 cm), but the fractional contributions were comparable. The comparison of mercury fractionation results obtained in this study for highly polluted soils with results of fractionation of uncontaminated or moderately contaminated samples of soil and sediments had not shown significant statistical differences; however, in the last samples elemental mercury is usually present at very low concentrations. On the basis of obtained correlation coefficients it seems that elemental mercury soils from “Areometer” plant are contaminated; the main transformation is its vaporization to atmosphere and oxidation to divalent mercury, probably mainly mediated by organic matter, and next bound to humic matter and sulfides.     

Mercury distribution, partitioning and speciation in coastal vs. inland High Arctic snow

Atmospheric mercury deposition on snow at springtime has been reported in polar regions, potentially posing a threat to coastal and inland ecosystems receiving meltwaters. However, the post-depositional fate of Hg in snow is not well known, and no data are available on Hg partitioning in polar snow. During snowmelt, we conducted a survey of Hg concentrations, partitioning and speciation in surface snow and at depth, over sea ice and over land along a 100 km transect across Cornwallis Island, NU, Canada. Total Hg concentrations [THg] in surface snow were low (less than 20 pmol L⁻¹) and were significantly higher in marine vs. inland environments. Particulate Hg in surface snow represented up to 90% of total Hg over sea ice and up to 59% over land. At depth, [THg] at the snow/sea ice interface (up to 300 pmol L⁻¹) were two orders of magnitude higher than at the snow/lake ice interface (ca. 2.5 pmol L⁻¹). Integrated snow columns, sampled over sea-ice and over land, showed that particulate Hg was mostly bound to particles ranging from 0.45 to 2.7 μm. Moreover, melting snowpacks over sea ice and over lake ice contribute to increase [THg] at the water/ice interfaces. This study indicates that, at the onset of snowmelt, most of the Hg in snow is in particulate form, particularly over sea ice. Low Hg levels in surface snow suggest that Hg deposited through early spring deposition events is partly lost to the atmosphere from the snowpack before snowmelt. The sea ice/snow interface may constitute a site for Hg accumulation, however. Further understanding of the cycling of mercury at the sea ice/snow and sea ice/seawater interfaces is thus warranted to fully understand how mercury enters the arctic food webs.     

Changes in Zn speciation during soil formation from Zn-rich limestones

In order to better understand the long-term speciation and fractionation of Zn in soils, we investigated three soils naturally enriched in Zn (237–864 mg/kg Zn) from the weathering of Zn-rich limestones (40–207 mg/kg Zn) using extended X-ray absorption fine structure (EXAFS) spectroscopy and sequential extractions. The analysis of bulk EXAFS spectra by linear combination fitting (LCF) indicated that Zn in the oolitic limestones was mainly present as Zn-containing calcite (at site Dornach), Zn-containing goethite (Gurnigel) and Zn-containing goethite and sphalerite (Liestal). Correspondingly, extraction of the powdered rocks with 1 M NH₄-acetate at pH 6.0 mobilized only minor fractions of Zn from the Gurnigel and Liestal limestones (<30%), but most Zn from the Dornach rock (81%). In the Dornach soil, part of the Zn released from the dissolving limestone was subsequently incorporated into pedogenic hydroxy-interlayered vermiculite (Zn-HIV, 30%) and Zn-containing kaolinite (30%) and adsorbed or complexed by soil organic and inorganic components (40%). The Gurnigel and Liestal soils contained substantial amounts of Zn-containing goethite (50%) stemming from the parent rock, smaller amounts (20%) of Zn-containing kaolinite (and possibly Zn-HIV), as well as adsorbed or complexed Zn-species (30%). In the soil from Liestal, sphalerite was only found in trace amounts, indicating its dissolution during soil formation. In sequential extractions, large percentages of Zn (55–85%) were extracted in recalcitrant extraction steps, confirming that Zn-HIV, Zn-containing kaolinite and Zn-containing goethite are highly resistant to weathering. These Zn-bearing phases thus represent long-term hosts for Zn in soils over thousands of years. The capability of these phases to immobilize Zn in heavily contaminated soils may however be limited by their uptake capacity (especially HIV and kaolinite) or their abundance in soil.     

Transformation of metal speciation in purple soil as affected by waterlogging

This study was conducted to investigate the effect of waterlogging on copper, lead and cadmium fractionation in Chinese purple soil. Heavy metals were added to purple soil at 80 % field capacity and waterlogging regimes as nitrate salts of 500 mg kg^?1 of copper and lead, and 5 mg kg^?1 of cadmium. Metals in the incubated soil samples were fractionated termly from 1 to 35 days by the sequential extraction procedure. Under both treatments, the heavy metals spiked in the soil were transformed slowly from the exchangeable fractions into more stable fractions, whereas their residual fractions barely changed. The transformation process of exchangeable fraction in soil was estimated by Elovich kinetic equation for the above incubation periods, and the constant B in Elovich equation was applied to reflect the transformation rates of metal speciation. It was found that waterlogging incubation could immobilize heavy metals, resulting in decreased lability and availability of the metals in purple soil. The effect of waterlogging on the redistribution of heavy metals in purple soil might be mainly related to the changes of pH, potential redox and hydrous oxides in varying soil-water systems.     

Mercury content of the Springfield coal, Indiana and Kentucky

With pending regulation of mercury emissions in United States power plants, its control at every step of the combustion process is important. An understanding of the amount of mercury in coal at the mine is the first step in this process. The Springfield coal (Middle Pennsylvanian) is one of the most important coal resources in the Illinois Basin. In Indiana and western Kentucky, Hg contents range from 0.02 to 0.55 ppm. The variation within small areas is comparable to the variation on a basin basis. Considerable variation also exists within the coal column, ranging from 0.04 to 0.224 ppm at one Kentucky site. Larger variations likely exist, since that site does not represent the highest whole-seam Hg nor was the collection of samples done with optimization of trace element variations in mind. Estimates of Hg capture by currently installed pollution control equipment range from 9–53% capture by cold-side electrostatic precipitators (ESP) and 47–81% Hg capture for ESP + flue-gas desulfurization (FGD). The high Cl content of many Illinois basin coals and the installation of Selective Catalytic Reduction of NO_x enhances the oxidation of Hg species, improving the ability of ESPs and FGDs to capture Hg.     

Regional and economic geology of Pennsylvanian age coal beds of West Virginia

West Virginia is the only place in the United States where an entire section of Pennsylvanian age (Upper Carboniferous) strata can be seen. These strata occur within a wedge of rock that thins to the north and west from the southeastern part of the State. The progressive north-northwesterly termination of older Pennsylvanian geologic units beneath younger ones prominently outlines the center of the Appalachian basin of West Virginia. Over most of West Virginia, Lower and/or Middle Pennsylvanian strata unconformably overly Upper Mississippian (Lower Carboniferous) strata. Sediment deposition was accomplished by a complex system of deltas prograding north and west from an eastern and southeastern source area.More than 100 named coal beds occur within the Lower, Middle, and Upper Pennsylvanian rocks of West Virginia and at least 60 of these have been or are currently being mined commercially. Collectively, these coal beds account for original in-ground coal resources of almost 106.1×10⁹ t (117×10⁹ tons). West Virginia ranks fourth in the United States in demonstrated coal reserves. In 1988, West Virginia produced 131.4×10⁶ t (144.9×10⁶ T) of coal, third highest in the United States. Of this annual production, 75% was from underground mines. In 1988, West Virginia led the nation in the number of longwall mining sections currently in place. West Virginia's low-volatile coal beds are known worldwide as important metallurgical-grade coals, while the higher-volatile coal beds are utilized primarily for steam production.