Harry E. Lerch

Health impacts of coal and coal use: possible solutions

Abstract Coal will be a dominant energy source in both developed and developing countries for at least the first half of the 21st century. Environmental problems associated with coal, before mining, during mining, in storage, during combustion, and postcombustion waste products are well known and are being addressed by ongoing research. The connection between potential environmental problems with human health is a fairly new field and requires the cooperation of both the geoscience and medical disciplines. Three research programs that illustrate this collaboration are described and used to present a range of human health problems that are potentially caused by coal. Domestic combustion of coal in China has, in some cases, severely affected human health. Both on a local and regional scale, human health has been adversely affected by coals containing arsenic, fluorine, selenium, and possibly, mercury. Balkan endemic nephropathy (BEN), an irreversible kidney disease of unknown origin, has been related to the proximity of Pliocene lignite deposits. The working hypothesis is that groundwater is leaching toxic organic compounds as it passes through the lignites and that these organics are then ingested by the local population contributing to this health problem. Human disease associated with coal mining mainly results from inhalation of particulate matter during the mining process. The disease is Coal Workers Pneumoconiosis characterized by coal dust-induced lesions in the gas exchange regions of the lung; the coal workers “black lung disease”.

Pyrolysis g.c.—m.s. of a series of degraded woods and coalified logs that increase in rank from peat to subbituminous coal☆

Xylem tissue from degraded wood and coalified logs or stems was examined by pyrolysis g.c.-m.s. to improve understanding of the coalification process. The pyrolysis data, when combined with solid-state 13C n.m.r. data for the same samples, show several stages of evolution during coalification. The first stage, microbial degradation in peat, involves the selective degradation of cellulosic components and preservation of lignin-like components. As coalification increases, the lignin structural units undergo a series of defunctionalization reactions. The first of these involve loss of methoxyl groups, with replacement by phenolic hydroxyls such that catechol-like structures are produced. As the xylem tissue is converted to subbituminous coal, the persistence of phenols and methylated phenols in pyrolysis g.c.-m.s. data of subbituminous coal suggests that the catechol-like structures are being converted to phenol-like structures. The ability to discern detailed changes in the chemical structural composition of a genetically and histologically related series of samples provides an ideal method for developing models of coal structure, especially that of low-rank coal.

Experimental early-stage coalification of a peat sample and a peatified wood sample from Indonesia

Abstract Experimental coalification of a peat sample and a buried wood sample from domed peat deposits in Indonesia was carried out to examine chemical structural changes in organic matter during early-stage coalification. The experiment (125°C, 408 atm lithostatic pressure, and 177 atm fluid pressure for 75 days) was designed to maintain both lithostatic and fluid pressure on the sample, but allow by-products that may retard coalification to escape. We refer to this design as a geologically open system. Changes in the elemental composition, and 13 C NMR and FTIR spectra of the peat and wood after experimental coalification suggest preferential thermal decomposition of O-containing aliphatic organic compounds (probably cellulose) during early-stage coalification. The elemental compositions and 13 C NMR spectra of the experimentally coalified peat and wood were generally similar to those of Miocene coal and coalified wood samples from Indonesia. Yields of lignin phenols in the peat and wood samples decreased following experimental coalification; the wood sample exhibited a larger change. Lignin phenol yields from the experimentally coalified peat and wood were comparable to yields of lignin phenols from Miocene Indoesian lignite and coalified wood. Changes in syringyl/vanillyl and p -hydroxy/vanillyl ratios suggest direct demethoxylation as a secondary process to demethylation of methoxyl groups during early coalification, and changes in lignin phenol yields and acid/aldehyde ratios point to a coupling between demethoxylation processes and reactions in the alkyl side chain bonds of the α-carbon in lignin phenols.

Studies of angiospermous wood in Australian brown coal by nuclear magnetic resonance and analytical pyrolysis: new insights into the early coalification process

Abstract Many Tertiary coals contain abundant fossilized remains of angiosperms that often dominated some ancient peat-swamp environments; modern analogs of which can be found in tropical and subtropical regions of the world. Comparisons of angiospermous woods from Australian brown coal with similar woods buried in modern peat swamps of Indonesia have provided some new insights into coalification reactions. These comparisons were made by using solid-state 13 C nuclear magnetic resonance (NMR) techniques and pyrolysis-gas chromatography-mass spectrometry (py-gc-ms), two modern techniques especially suited for detailed structural evaluation of the complex macromolecules in coal. From these studies, we conclude that the earliest transformation (peatification) of organic matter in angiospermous wood is the degradation of cellulosic components. The efficiency of removal of cellulosic components in the wood varies considerably in peat, which results in variable levels of cellulose in peatified wood. However, the net trend is towards eventual removal of the cellulose. The angiospermous lignin that becomes enriched in wood as a result of cellulose degradation also is modified by coalifications reactions; this modification, however, does not involve degradation and removal. Rather, the early coalification process transforms the lignin phenols (guaiacyl and syringyl) to eventually yield the aromatic structures typically found in brown coal. One such transformation, which is determined from the NMR data, involves the cleavage of aryl ether bonds that link guaiacyl and syringyl units in lignin and leads to the formation of free lignin phenols. Another transformation, which is also determined from the NMR data, involves the loss of methoxyl groups, probably via demethylation, to produce catechol-like structures. Coincident with ether-cleavage and demethylation, the aromatic rings derived from lignin phenols become more carbon-substituted and cross-linked, as determined by dipolar-dephasing NMR studies. This cross-linking is probably responsible for preventing the lignin phenols, which are freed from the lignin macromolecule by ether cleavage and from being removed from the coal by dissolution. Pyrolysis data suggest that the syringyl units are altered more readily than are guaiacyl units, which leads to an enrichment of the guaiacyl units in fossil angiospermous woods. Although many of the coalification reactions noted above occur to some degree in all angiospermous fossil woods examined, some significant differences are observed in the degree of coalification of the fossil woods from the same burial depth in the brown coal. This indicates that the depth and the duration of burial are probably not entirely responsible for the variations in degree of coalification. It is likely that different rates of degradation in peat may have contributed to the variations in the apparent degree of coalification, considering the fact that some woods may have been altered more rapidly at the peat stage than others. Although preliminary, it is clear that a systematic study of botanically related woods in peat and coal leads to a more detailed differentiation of coalification reactions than have previous investigations. The combined use of solid-state 13 C NMR and py-gc-ms has facilitated this detailed new insight into coalification of angiospermous wood.

Solid-state 13C nuclear magnetic resonance studies of coalified gymnosperm xylem tissue from Australian brown coals

We report here on the use of solid-state 13C nuclear magnetic resonance (NMR) spectroscopy to contrast the average chemical composition of modern degraded gymnosperm woods with fossil gymnosperm woods from Australian brown coals (Miocene). We first established the quantitative nature of the NMR techniques for these samples so that the conventional solid-state 13C NMR spectra and the dipolar dephasing NMR spectra could be used with a high degree of reliability to depict average chemical compositions. The NMR results provide some valuable insights about the early coalification of xylem tissue from gymnosperms. Though the cellulosic components of wood are degraded to varying degrees during peatification and ensuing coalification, it is unlikely that they play a major role in the formation of aromatic structures in coalified woods. The NMR data show that gynmosperm lignin, the primary aromatic contribution to the coal, is altered in part by demethylation of guaiacyl-units to catechol-like structures. The dipolar dephasing NMR data indicate that the lignin also becomes more cross-linked or condensed.

Lignin phenols in sediments of Lake Baikal, Siberia: Application to paleoenvironmental studies

Sediments from three cores obtained from distinct depositional environments in Lake Baikal, Siberia were analyzed for organic carbon, total nitrogen and lignin phenol concentration and composition. Results were used to examine changes in paleoenvironmental conditions during climatic cycles of the late Quaternary (< 125 ka). Average organic carbon, and total nitrogen concentrations, atomic C/N ratios and organic carbon accumulation rates were significantly higher in the Holocene compared with the late Pleistocene, reflecting overall warmer temperatures and increased runoff during the Holocene. A Holocene maximum in organic carbon was observed at about 6 ka, and may represent the warmest/ wettest period of the Holocene. At one site (Academician Ridge) pronounced late Pleistocene maxima in organic carbon and biogenic silica were observed at about 80-85 ka, probably indicative of an interstadial period with enhanced aquatic productivity. Total sedimentary lignin phenol contents were generally lower in the late Pleistocene compared to the Holocene, but with several peaks in concentration during the late Pleistocene. These late Pleistocene peaks in total sedimentary lignin content (dated at about 80, 50 and 30 ka) directly precede or occur during peaks in sedimentary biogenic silica contents. These periods likely represent relatively warm interstadial times, with increased precipitation producing the observed increase in terrestrial runoff and aquatic productivity. Lignin phenol ratios (S/V, C/V and P/V) were used to examine changes in terrestrial vegetation type resulting from changes in paleoenvironmental conditions during the late Pleistocene. A degree of caution must be used in the interpretation of these ratios with regard to vegetation sources and paleoenvironmental conditions, because of potential compositional changes in lignin resulting from biodegradation. Nevertheless, results show that long glacial periods were characterized by terrestrial vegetation composed of a mix of non-woody angiosperm vegetation and minor gymnosperm forest. Shorter interstadial periods are defined by a change to dominant gymnosperm forest and were observed at about 80, 75, 63, 50 and 30 ka, ranging from about 2-6 kyr in duration. These interstadial periods of the late Pleistocene defined by lignin phenol ratios generally occur during longer periods of enhanced sedimentary biogenic silica content (about 10-15 ka in duration), providing corroborative evidence of these warm interstadial periods.

1,3,5-Hydroxybenzene structures in mosses

Abstract A number of mosses from widely different families have been studied by cross polarization solid state 13 C NMR spectroscopy. Although polysaccharide-type materials dominate the NMR spectra, significant amounts of aromatic carbons are observed in some mosses. Some of this material can be removed by ultrasonic bath treatment, and is lignin derived, probably from impurities from fine root material from associated higher plants. However other material is truly moss-derived and appears to be from 1,3,5-hydroxybenzene structures. This is inconsistent with lignin as being a component of mosses, and suggests a tannin or hydroxybenzofuran polymer is responsible for moss rigidity.

Organic geochemical studies of the transformation of gymnospermous xylem during peatification and coalification to subbituminous coal

Abstract It is generally recognized that xylem from trees that are buried in peat swamps is transformed first to huminite macerals in brown coal and then to vitrinite macerals in bituminous coal by processes collectively known as coalification. In order to understand the chemical nature of coalification of xylem and the chemical structures that eventually evolve in coal, we examined a series of gymnospermous xylem samples coalified to varying degrees. The samples included modern fresh xylem, modern degraded xylem in peat, and xylem coalified to ranks of brown coal (lignite B), lignite A, and subbituminous coal. The organic geochemical methods used in this study included solid-state 13 C nuclear magnetic resonance (NMR) and pyrolysis/gas chromatography/mass spectrometry. The NMR method provided average compositional information, and the pyrolysis provided detailed molecular information. Although the samples examined include different plants of different geologic ages, they all share a common feature in that they are gymnospermous and presumably have or had a similar kind of lignin. The data obtained in this study provide enough details to allow delineation of specific coalification pathway for the xylem is microbial degradation in peat (peatification), leading to selective removal of cellulosic components. These components constitute a large fraction of the total mass of xylem, usually greater than 50%. Although cellulosic components can survive degradation under certain conditions, their loss during microbial degradation is the rule rather than exception during peatification. As these components of xylem are degraded and lost, lignin, another major component of xylem, is selectively enriched because it is more resistant to microbial degradation than the cellulosic components. Thus, lignin survives peatification in a practically unaltered state and becomes the major precursor of coalified xylem. During its transformation to brown coal and lignite A, lignin in xylem is altered by two important processes. The first involves loss of methoxyl groups, primarily by demethylation (Fig. 1A). The end products of demethylation are catechol-like structures as shown below in Figure 1B. The second transformation process involves increased cross-linking of the aromatic rings. This cross-linking induces increased carbon substitution of the aromatic rings such that the lignin-derived structures become more highly condensed. During its conversion to coalified xylem in subbituminous coal, lignitic xylem, composed primarily of condensed catechol-like structures, is transformed to a macromolecular material primarily composed of phenol-like structures. The catechol-like structures of lignitic xylem loose a hydroxyl group, which is replaced by a hydrogen to form the phenol-like structure as shown in the example in Figure 1B. The pyrolysis data provided only a few clues as to the fate of the C 3 -side chain of lignin during coalification. However, the NMR data suggest that this side chain is altered, probably by loss of the hydroxyl groups that are attached in modern lignin. Interference in the NMR analysis by aliphatic components of wood, such as resins, precludes definitive determinations of the fate of the C 3 -side chain during coalification.

Nutrient Geochemistry of Sediments from Two Tree Islands in Water Conservation Area 3B, the Everglades, Florida

Sediment cores from two tree islands (Nuthouse and Gumbo Limbo) located in Water Conservation Area 3B of the Everglades, Florida were examined for preliminary studies of their nutrient geochemistry and paleoecology. Cores were collected from sites on the head, tail, and surrounding slough/marsh at each of the islands, and sediments from these cores were analyzed for various chemical constituents. Porewater in cores collected from the head and surrounding slough/marsh was also analyzed for its chemical composition for the purpose of evaluating nutrient recycling from tree island heads. Intervals in selected cores from both tree islands were dated using 14C analysis. The major objectives of the study were to: 1) determine the concentrations and accumulation rates of nutrients (carbon, nitrogen, and phosphorus) in sediments of tree islands, 2) examine the role of nutrients (if any) in the development of tree island tails and 3) examine downcore trends in nutrient element concentrations for evidence of ecological changes through time.

Studies of a peatified angiosperm log cross section from Indonesia by nuclear magnetic resonance spectroscopy and analytical pyrolysis

Samples from a 10 cm cross-sectional radius of a peatified angiosperm log from Sumatra, Indonesia, were examined by 13C nuclear magnetic resonance and pyrolysis-gas chromatography in order to understand chemical changes due to the peatification process. NMR results show degradation by selective loss of carbohydrates in all parts of the log section compared with fresh wood; however, the degree of degradation is less near the center of the log section. The degree of ring substitution of aromatic lignin monomeric units, as measured by dipolar dephasing NMR methods, appears to be less at the center of the log section than at the periphery. The methoxyl carbon content of lignin in the log is lower than in unaltered angiospermous lignin but does not appear to change as a function of either radial position or the degree of aromatic ring substitution. Pyrolysis-gas chromatography indicates higher yields of catechols in the outer areas relative to the heartwood. Other than the variations in catechol contents and in the yields of carbohydrate-derived pyrolysis products (e.g. levoglucosan, angelicalactones), the pyrolysis results do not show significant changes related to radial position, indicating that the lignin is not significantly altered across the log section.