Distribution of rare earth elements in PM10 emitted from burning coals and soil-mixed coal briquettes.

Emission from burning coals is one of the major sources of the airborne particles in China. We carried out a study on the rare earth elements (REEs) in the inhalable particulate matter (PM10) emitted from burning coals and soil-coal honeycomb briquettes with different volatile contents and ash yields in a combustion-dilution system. Gravimetric analysis indicates that the equivalent mass concentration of the PM10 emitted from burning the coals is higher than that emitted from burning the briquettes. The ICP-MS analysis indicates that the contents of total REEs in the coal-burning PM10 are lower than those in the briquette-burning PM10. In addition, the contents of the light rare earth elements (LREEs) are higher than those of the heavy rare earth elements (HREEs) in the PM10 emitted from burning the coals and briquettes, demonstrating that the REEs in both the coal-burning and briquette-burning PM10 are dominated by LREEs. The higher contents of total REEs and LREEs in the coal-burning PM10 are associated with the higher ash yields and lower volatile contents in the raw coals. A comparative analysis indicates that the La/Sm ratios in the PM10 emitted from burning the coals and briquettes, being lower than 2, are lower than those in the particles from gasoline-powered vehicle emission.

Laboratory studies of the impact of calcite on in vitro and in vivo effects of coal dust: a potential preventive agent for coal workers' pneumoconiosis?

BACKGROUND: Bioavailable iron (BAI) in coal, which may play a key role in causing coal workers' pneumoconiosis (CWP), is present at relatively high levels in Appalachian coals. Calcite decreases BAI and is more plentiful in Western coals than in Appalachian coals, possibly explaining the lower CWP prevalence among Western miners. METHODS: We measured effects of calcite on BAI in non-cellular and cellular systems involving Pennsylvania (PA) coal dust. We also tested in vivo effects of calcite on transferrin receptor and markers of epithelial mesenchymal transition (EMT) and inflammation in mice exposed to PA coal. RESULTS: Calcite rapidly eliminated BAI in an aqueous suspension of PA coal. Ferritin induction in human lung epithelial cells exposed to PA coal was effectively eliminated by calcite. Mouse lung tissue markers indicated increased EMT after exposure to PA coal dust, but not after exposure to PA coal plus calcite. Markers of inflammation increased following exposure to PA coal alone, but not following exposure to PA coal plus calcite. CONCLUSION: Additional research may lead to the use of supplemental calcite in coal mining as a safe and effective way to prevent CWP among Appalachian coal miners.

Analysis of multiple pathways and levels of fluoride intake in fluorosis areas of Southwest China.

In the coal-burning fluorosis areas of China, over 10 million people suffer from dental fluorosis caused by multiple pathways of fluoride intake. However, the link between dental fluorosis prevalence, the geochemical distribution of fluoride, and contributions of different exposure pathways remain unclear. Here, we aimed to quantify the various fluoride exposure pathways and establish the association between dental fluorosis and fluoride intake in Southwest China. Epidemiological data on the peak time of fluorosis prevalence were combined with geochemical analyses of the fluoride content in coal and clay over a large scale, the amounts and ratios of fluoride intake through different exposure pathways were calculated, and the association between the total daily fluoride intake (TDFI) and dental fluorosis severity was analyzed. The prevalence of dental fluorosis was not significantly correlated with the fluoride geo-background of coal and clay on a large scale (P > 0.05). The co-combustion of coal and clay contained in hand-made briquettes is the main pathway of fluoride contamination, which occurs through the inhalation of polluted air and consumption of contaminated roasted products. Furthermore, the TDFI per person ranged from 2.78 to 17.32 mg, and it was significantly positively correlated with the prevalence of dental fluorosis (P < 0.05). The TDFI from breathing and eating was 1.1-3.2 mg and 1.1-15.1 mg, which accounted for 9%-54% and 40%-90% of the total TDFI, respectively. The combination of living habits and soil geochemical fluoride anomalies resulted in the higher prevalence of fluorosis in rural areas of Southwest China.

Advocating the Use of Bayesian Network in Analyzing the Modes of Occurrence of Elements in Coal.

Modes of occurrence of elements in coal are important because they can be used not only to understand the origin of inorganic components in coal but also to determine the impact on the environment and human health and the deposition process of coal seams as well. Statistical analysis is one of the commonly used indirect methods used to analyze the modes of occurrence of elements in coal, among which hierarchical clustering is widely used. However, hierarchical clustering may lead to misleading results due to its limitation that it focuses on the clusters of elements rather than a single element. To tackle this issue, we use the first part of a well-known Bayesian network structure learning algorithm, i.e., Peter-Clark (PC) algorithm, to explore the relationships of the coal elemental data and then infer modes of occurrence of elements in coal. A data set containing 95 Late Paleozoic coal samples from the Datanhao and Adaohai mines in Inner Mongolia, China, is used for the performance evaluation. Analytical results show that many instructive and surprising insights can be concluded from the first part of the PC algorithm. Compared with the hierarchical clustering algorithm, the first part of the PC algorithm demonstrates superiority in analyzing the modes of occurrence of elements in coal.

A review of the mineralogical and chemical composition of nanoparticles associated with coal fires.

This review summarizes our current knowledge on the health and environmental impact as well as the mineralogical and geochemical composition of nanoparticles (NPs) associated with coal fires. It will furthermore recommend new sampling and characterization protocols to gain a better understanding of the various types of NPs that are formed either through high-temperature nucleation and alteration processes or via low-temperature dissolution-reprecipitation and weathering processes. Coal fires affect the immediate environment of coal-producing areas and produce positive and negative feedback to climate change through the emission of carbon- and sulfate-bearing gases and aerosols, respectively. Nanoparticles form during and after coal fires. They are composed of mainly soot and tar particles as well as amorphous phases, minerals, and complex mixtures of amorphous phases and minerals. It is recommended that NPs for mineralogical studies should be collected using impactors (a new generation of collectors for particulate matter, such as the TPS100 NP sampler) or that borosilicate filters at the openings of pipes and chambers be used to collect and measure gases emitted by coal fires. Furthermore, assemblages of NPs occurring at the mouths of coal fire vents should be examined using a combination of focused ion beam (FIB) technology and transmission electron microscopy (TEM), and those containing ion- or electron-beam sensitive phases should be examined with the corresponding cryo-techniques, such as cryo-FIB, cryo-ion mill, and cryo-TEM. The mineralogical and chemical composition of NP-bearing bulk samples should be examined with spectroscopy techniques such as X-ray photoelectron spectroscopy, 13 C nuclear magnetic resonance spectroscopy, or time-of-flight secondary ion mass spectroscopy.

Leaching of potential hazardous elements of coal cleaning rejects.

The geochemical characteristics of coal cleaning rejects (CCR) in Santa Catarina State, Brazil, were investigated. Around 3.5 million ton/year of coal waste are dumped in Santa Catarina State. Coal beneficiation by froth flotation results in large amounts of CCR composed of coaly and mineral matter, the latter characterised by the occurrence of sulphide minerals and a broad array of leachable elements. The total and leachable contents of more than 60 elements were analysed. Atmospheric exposure promotes sulphide oxidation that releases substantial sulphate loads as well as Ca2+, K+, Mg2+, Cl- and Al3+. The metals with the most severe discharges were Zn, Cu, Mn, Co, Ni and Cd. Most trace pollutants in the CCR displayed a marked pH-dependent solubility, being immobile in near-neutral samples. The results highlight the complex interactions among mineral matter solubility, pH and the leaching of potentially hazardous elements.

Average Linkage Hierarchical Clustering Algorithm for Determining the Relationships between Elements in Coal.

The modes of occurrence of elements in coal are important not only because they can provide insights into the sources of mineral matter in coal but also because they are vital in determining the behavior of their environmental and human health impacts. Besides a number of physical and chemical analyses for determining the modes of occurrence in coal, some statistical methods have been commonly adopted to investigate elements in coal. Among many statistical methods, the hierarchy clustering algorithm is the most common method for deducing modes of occurrence of elements in coal. However, different hierarchical clustering algorithms with a number of similarity measures sometimes result in different modes of occurrence of elements in coal, and subsequently in some cases, such results could be confusing. Therefore, which algorithm is more effective in determining the modes of occurrence in coal deserves to be investigated. In this paper, the data sets of coals from the Adaohai coal mine in Inner Mongolia, China, are used for this performance evaluation. From the analytical results with the average linkage hierarchical clustering algorithm on Adaohai coal samples, many instructive and surprising insights can be concluded. For example, selenium, Be, and Tl do not appear to be in agreement with geochemical principles, that is, substituting for P, associated with rare earth elements, and occurring in Fe-sulfides, respectively. In conclusion, the average linkage hierarchical clustering algorithm with correlation similarity is much better in the analysis of the geological processes than the previous statistical method used in Adaohai coal samples, that is, centroid linkage hierarchical clustering algorithm with Pearson correlation similarity.

Measurements of the leachability of potentially hazardous trace elements from solid coal gasification wastes in China.

Solid wastes from commercial coal gasification plants are a significant environmental issue in China because of the large quantities produced. In recent years, with the rapid development of coal gasification technologies in China, more and more coal gasification residues are being disposed of in landfills because of the low utilization of the residues. In the present study, the column leaching procedure M1314 developed by the U.S. Environmental Protection Agency was used to evaluate the potential for environmental pollution by potentially hazardous trace elements (Be, V, Mn, Cr, Co, Ni, Cu, Zn, As, Se, Sr, Mo, Cd, Sb, Cs, Ba, Tl, Pb, Hg, Th, and U) in the coarse and fine gasification residues from two plants using General Electric (GE) and Gaskombinat Schwarze Pumpe (GSP) coal gasification technologies in northwest China. The potentially hazardous trace elements in the residues show different release patterns with the liquid-solid ratio increasing. The cumulative leached concentrations of the potentially hazardous trace elements from the coal gasification residues were generally low, and only Mo in the leachate of GSP fine residue was moderately soluble. V in the GSP coal gasification residues showed an increasing leachability in the leaching procedure. As, Se, Mo, Sb, and Tl in some leachates exceeded their thresholds in Level III of the Chinese Quality Standard for Groundwater and/or the Maximum Contaminant Levels of the U.S. National Primary Drinking Water Regulations. According to the risk assessment code, Se in the GE fine residue and Mo in the GE and GSP fine residues had medium risk to the ecosystem. Those data indicated that the potential for environmental pollution by those elements from coal gasification plants should be given consideration.

Evaluation of carbon forms and elements composition in coal gasification solid residues and their potential utilization from a view of coal geology.

As the development of coal gasification technology expands in China, the resulting solid by-products can become environmental and economic concerns. Evaluation of carbon forms and elemental composition in coal gasification solid residues from three advanced commercial-scale entrained-flow gasification plants in China related to feedstock coal properties are studied and their potential utilization is discussed in the present study. The properties of the residues of the three entrained-flow gasification processes differed as a result of the type of process applied, even though the properties of their feedstocks are similar. Eight types of carbon forms were identified. The high-inertinite feedstock resulted in a fusinite-like carbon being the primary carbon form of the residues, except for the General Electric fine residue (GE-FR) sample. The carbon contents of the coarse residues (CRs) produced from the Opposed Multi-Burner (OMB) coal-water slurry gasifier and the Gaskombiant Schwarze Pumpe (GSP) pulverized coal gasifier are comparable, lower than 2% (Cd), but a high content of carbon present as "black particles" (79.90%, Cd) was concentrated from the OMB-CR sample. Fourier transform infrared spectroscopy (FTIR) analyses indicate that the main functional group of the fusinite-like material in OMB-CR is methyl (CH3-). From the chemical composition point of view, the high proportions of F2O3 and CaO in the GE residues make them potential sources of high-Fe or high-Ca material. The relatively high concentrations of In, Ga, Sb, Cs, Cr, Ba, and rare earth elements in the residues make them potential raw materials for extracting critical trace elements, especially the OMB-FR and GSP-FR samples for extracting Ga.

Heavy metal distribution in soils near Palapye, Botswana: an evaluation of the environmental impact of coal mining and combustion on soils in a semi-arid region.

Morupule Colliery near Palapye in eastern Botswana is the only coalmine in production in Botswana at present. Its coal is mainly used in the nearby coal-fired Morupule Power Station, which generates approximately 1,000 GWh of electricity per annum. After more than 30 years mining and more than 20 years of combustion, the sedimentation of outlet fly ash from the Morupule Power Station has increased concentrations of Cr, Ni, Zn and As by 13, 2.5, 16 and 5 ppm, respectively, in the fine portion (<53 µm) of surface soils for approximately 9 km downwind. Elements that have higher concentrations in coal have stronger small-particle association during coal combustion and are less mobile in surface soils, thus showing stronger contaminations in surface soils around the coal-fired plant. Although the degree of contamination of Cr, Ni, Zn and As from coal combustion in the Palapye area at present is low, it is necessary to monitor concentrations of these elements in surface soils routinely in the future. This study also reveals moderate Pb and Zn contaminations in the Palapye area. The former is due to the use of leaded petroleum in motor vehicle traffic and the latter is mainly due to the use of galvanized iron sheets in construction.

Fate of potentially hazardous trace elements during the entrained-flow coal gasification processes in China.

With the rapid and wide application of the coal gasification technology in China, the corresponding environmental issues require increasing attention. In this study, the feed coal, coal gasification wastewater samples at key technical links, and the coal gasification residues were collected from three entrained-flow coal gasification plants in Northwest China and were characterized to understand the migration and partition of 21 potentially hazardous trace elements (PHTEs) in coal gasification process and their potential environmental impacts. Compared with Chinese coal, the concentrations of the PHTEs in the feed coals are mainly at the level of "depleted" and "normal". Undergoing the heating process in the gasifier, purification procedure for the syngas, and the residue-wastewater separation, the PHTEs in the feed coals are transferred into gaseous phase, wastewater, and gasification residues. The PHTEs are easier to be released into the gaseous phase during the GSP gasification process compared with the OMB and GE gasification processes. The chalcophile elements Zn, As, Se, Cd, Sb, Tl, Pb, and Hg tend to be enriched in the fine residues, and the retention capability of Hg by the residues is the lowest. With the grey water circulation and the use of additives, the black water samples have higher PHTEs concentrations than other water samples. Except for Sr, Mo, Sb, and Cs, most of the elements in the original water samples can be reduced effectively by removing the particulate matters. In some cases, Cr6+, Zn, As, Se, Cd, and Pb in the original wastewater samples exceed the limit for industrial use as indicated in the Chinese Environmental Quality Standards for Surface Water and the Emission Standard for Pollutants from Coal Industry. The potential environmental impacts of As and Se in the water cannot be reduced by filtration. The environmental impacts of the coal gasification residues should be further evaluated.

Understanding the chemical properties of macerals and minerals in coal and its potential application for occupational lung disease prevention.

Recent increases in oil price further strengthen the argument that coal and coal products will play an increasingly important role in fulfilling the energy needs of our society. Coal is an aggregate of heterogeneous substances composed of organic (macerals) and inorganic (minerals) materials. The objective of this review was to assess whether some chemical parameters in coal play a role in producing environmental health problems. Basic properties of coal--such as chemical forms of the organic materials, structure, compositions of minerals--vary from one coal mine region to another as well as from coals of different ranks. Most importantly, changes in chemical properties of coals due to exposure to air and humidity after mining--a dynamic process--significantly affect toxicity attributed to coal and environmental fate. Although coal is an extremely complex and heterogeneous material, the fundamental properties of coal responsible for environmental and adverse health problems are probably related to the same inducing components of coal. For instance, oxidation of pyrite (FeS2) in the coal forms iron sulfate and sulfuric acid, which produces occupational lung diseases (e.g., pneumoconiosis) and other environmental problems (e.g., acid mine drainage and acid rain). Calcite (CaCO3) contained in certain coals alters the end products of pyrite oxidation, which may make these coals less toxic to human inhalation and less hazardous to environmental pollution. Finally, knowledge gained on understanding of the chemical properties of coals is illustrated to apply for prediction of toxicity due to coal possibly before large-scale mining and prevention of occupational lung disease during mining.

Health benefits of geologic materials and geologic processes.

The reemerging field of Medical Geology is concerned with the impacts of geologic materials and geologic processes on animal and human health. Most medical geology research has been focused on health problems caused by excess or deficiency of trace elements, exposure to ambient dust, and on other geologically related health problems or health problems for which geoscience tools, techniques, or databases could be applied. Little, if any, attention has been focused on the beneficial health effects of rocks, minerals, and geologic processes. These beneficial effects may have been recognized as long as two million years ago and include emotional, mental, and physical health benefits. Some of the earliest known medicines were derived from rocks and minerals. For thousands of years various clays have been used as an antidote for poisons. "Terra sigillata," still in use today, may have been the first patented medicine. Many trace elements, rocks, and minerals are used today in a wide variety of pharmaceuticals and health care products. There is also a segment of society that believes in the curative and preventative properties of crystals (talismans and amulets). Metals and trace elements are being used in some of today's most sophisticated medical applications. Other recent examples of beneficial effects of geologic materials and processes include epidemiological studies in Japan that have identified a wide range of health problems (such as muscle and joint pain, hemorrhoids, burns, gout, etc.) that may be treated by one or more of nine chemically distinct types of hot springs, and a study in China indicating that residential coal combustion may be mobilizing sufficient iodine to prevent iodine deficiency disease.

Mapping and prediction of coal workers' pneumoconiosis with bioavailable iron content in the bituminous coals.

Based on the first National Study of Coal Workers' Pneumoconiosis (CWP) and the U.S. Geological Survey database of coal quality, we show that the prevalence of CWP in seven coal mine regions correlates with levels of bioavailable iron (BAI) in the coals from that particular region (correlation coefficient r = 0.94, p < 0.0015). CWP prevalence is also correlated with contents of pyritic sulfur (r = 0.91, p < 0.0048) or total iron (r = 0.85, p < 0.016) but not with coal rank (r = 0.59, p < 0.16) or silica (r = 0.28, p < 0.54). BAI was calculated using our model, taking into account chemical interactions of pyrite, sulfuric acid, calcite, and total iron. That is, iron present in coals can become bioavailable by pyrite oxidation, which produces ferrous sulfate and sulfuric acid. Calcite is the major component in coals that neutralizes the available acid and inhibits iron's bioavailability. Therefore, levels of BAI in the coals are determined by the available amounts of acid after neutralization of calcite and the amount of total iron in the coals. Using the linear fit of CWP prevalence and the calculated BAI in the seven coal mine regions, we have derived and mapped the pneumoconiotic potencies of 7,000 coal samples. Our studies indicate that levels of BAI in the coals may be used to predict coal's toxicity, even before large-scale mining.

The emerging Medical and Geological Association.

The impact on human health by natural materials such as water, rocks, and minerals has been known for thousands of years but there have been few systematic, multidisciplinary studies on the relationship between geologic materials and processes and human health (the field of study commonly referred to as medical geology). In the past few years, however, there has been a resurgence of interest in medical geology. Geoscientists working with medical researchers and public health scientists have made important contributions to understanding novel exposure pathways and causes of a wide range of environmental health problems such as: exposure to toxic levels of trace essential and non-essential elements such as arsenic and mercury; trace element deficiencies; exposure to natural dusts and to radioactivity; naturally occurring organic compounds in drinking water; volcanic emissions, etc. By linking with biomedical/public health researchers geoscientists are finally taking advantage of this age-old opportunity to help mitigate environmental health problems. The International Medical Geology Association has recently been formed to support this effort.