Quality assessment of biomass pellets available on the market; example from Poland.

This study evaluates the quality of 30 biomass pellets sold for residential use in Poland. It provides data on their physical, chemical, and petrographic properties and compares them to existing standards and the information provided by the fuel producers. The results reveal considerable variations in the quality of the pellets and show that some of the purchased samples are not within the DINplus and/or ENplus certification thresholds. Among all 30 purchased samples, only one passes the quality thresholds set by the PL-US BIO, a newly established quality certification in Poland that combines quality assessment following DINplus with optical microscopy analysis. The primary issues causing a decrease in pellet quality include elevated ash and fines content, compromised mechanical durability, too low ash melting temperature, and additions of undesired additions like bark, inorganic matter, and petroleum products. Our research highlights the need for improved fuel quality control measures, and transparent and accurate product labeling, as well as the need for a comprehensive and publicly available national database of solid biomass fuel producers and fuels sold. These are essential steps toward increasing customers' awareness and trust, encouraging them to embrace biomass fuels as reliable and sustainable sources of energy.

Diversity and Composition of Methanotroph Communities in Caves.

Methane oxidizing microorganisms (methanotrophs) are ubiquitous in the environment and represent a major sink for the greenhouse gas methane (CH4). Recent studies have demonstrated methanotrophs are abundant and contribute to CH4 dynamics in caves. However, very little is known about what controls the distribution and abundance of methanotrophs in subterranean ecosystems. Here, we report a survey of soils collected from > 20 caves in North America to elucidate the factors shaping cave methanotroph communities. Using 16S rRNA sequencing, we recovered methanotrophs from nearly all (98%) of the samples, including cave sites where CH4 concentrations were at or below detection limits (≤0.3 ppmv). We identified a core methanotroph community among caves comprised of high-affinity methanotrophs. Although associated with local-scale mineralogy, methanotroph composition did not systematically vary between the entrances and interior of caves, where CH4 concentrations varied. We also observed methanotrophs are able to disperse readily between cave systems showing these organisms have low barriers to dispersal. Lastly, the relative abundance of methanotrophs was positively correlated with cave-air CH4 concentrations, suggesting these microorganisms contribute to CH4 flux in subterranean ecosystems. IMPORTANCE Recent observations have shown the atmospheric greenhouse gas methane (CH4) is consumed by microorganisms (methanotrophs) in caves at rates comparable to CH4 oxidation in surface soils. Caves are abundant in karst landscapes that comprise 14% of Earth's land surface area, and therefore may represent a potentially important, but overlooked, CH4 sink. We sampled cave soils to gain a better understand the community composition and structure of cave methanotrophs. Our results show the members of the USC-γ clade are dominant in cave communities and can easily disperse through the environment, methanotroph relative abundance was correlated with local scale mineralogy of soils, and the relative abundance of methanotrophs was positively correlated with CH4 concentrations in cave air.

Environmental implications of the quality of charcoal briquettes and lump charcoal used for grilling.

Numerous studies have been conducted to assess air pollution and human health risks arising from exposure to outdoor cooking, but limited standards have been implemented around the world to assure fuel quality. While charcoal briquettes and lumps are a popular fuel choice for grilling, almost no data specifying their properties are available to consumers. Because the properties of fuels affect the flue gases, it is critical to understand how the quality of grilling briquettes and lumps translates not only into the quality of the grilled food, but, even more importantly, how their emissions impact human safety and the environment. The main purpose of this study is to investigate the impacts of the quality of charcoal briquettes and lumps on potentially harmful emissions during grilling. To analyze their quality, we used reflected light microscopy to identify a range of contaminants, including biomass, mineral matter, coal, coke, metal, rust, plastics, glues, and synthetic resins, in 74 commercially available products made in Poland, the United States of America, Ukraine, Germany, Belarus, the Czech Republic, and the Republic of South Africa. Our data show that majority of the products analyzed do not meet the existing quality standard EN 1860-2:2005 (E) of less than 1% contaminants, some of these products contain up to 26.6% of impurities. The amount of contaminants correlates with particulate matter, as well as CO and CO2. The contribution of biomass is especially significant because it can be used to predict harmful particulate matter emissions during grilling. The relationship between the composition of charcoal briquettes and lump charcoal and their emissions is particularly strong during the first 15 to 20 min after ignition (when emissions are the highest), therefore, this initial stage is especially unsafe to consumers, and staying away from the grill during this time is recommended.

Environmental forensic characterization of former rail yard soils located adjacent to the Statue of Liberty in the New York/New Jersey harbor.

Identifying inorganic and organic soil contaminants in urban brownfields can give insights into the adverse effects of industrial activities on soil function, ecological health, and environmental quality. Liberty State Park in Jersey City (N.J., USA) once supported a major rail yard that had dock facilities for both cargo and passenger service; a portion remains closed to the public, and a forest developed and spread in this area. The objectives of this study were to: 1) characterize the organic and inorganic compounds in Liberty State Park soils and compare the findings to an uncontaminated reference site (Hutcheson Memorial Forest); and 2) identify differences between the barren low-functioning areas and the forested high-functioning areas of the brownfield. Soil samples were solvent-extracted, fractionated, and analyzed by gas chromatography-mass spectrometry and subjected to loss-on-ignition, pyrolysis-gas chromatography-mass spectrometry, inductively-coupled-plasma mass spectrometry, and optical microscopy analyses. Compared to soil from the reference site, the forested soils in Liberty State Park contained elevated percentages of organic matter (30-45%) and more contaminants, such as fossil-fuel-derived hydrocarbons and coal particles. Microscopy revealed bituminous and anthracite coal, coke, tar/pitch, and ash particles. Barren and low-functioning site 25R had a similar organic contaminant profile but contained a higher metal load than other Liberty State Park sites and also lacked higher plant indicators. These can obscure the signatures of contaminants, and data from adjacent barren and vegetated sites are valuable references for soils studies. A deeper understanding of the chemistry, biochemistry, and ecology of barren soils can be leveraged to prevent land degradation and to restore dysfunctional and phytotoxic soils.

Natural geological seepage of hydrocarbon gas in the Appalachian Basin and Midwest USA in relation to shale tectonic fracturing and past industrial hydrocarbon production.

Geological hydrocarbon gas seepage is a major global source of atmospheric methane, ethane and propane as greenhouse gases and photochemical pollutants. Natural gas seepage is generally related to faults and associated fracture intensification domains that provide conduits for natural gas from reservoir rocks to migrate upward and enter the atmosphere. In this study, we compare the case of intense gas seepage stemming directly from source rocks, mostly organic-rich fractured black shales in western New York State (NYS) versus areas with rare seepage in the more southern regions of the Appalachian Basin and the Midwest USA. In addition to thermogenic methane, western NYS shale gas seeps emit ethane and propane with C2+3 gas concentrations reaching up to 35 vol%. Fractures in NYS developed, reactivated and maintained permeability for gas as a result of Quaternary glaciation and post-glacial basin uplift. In contrast, the Appalachian regions farther south and the southern Midwest regions experienced less glacial loading and unloading than in NYS, resulting in less recent natural fracturing, as witnessed by the rarity of seepage on surface outcrops and in caves overlying gas-bearing shales and coals. The historical literature suggests that early western NYS drilling and production of oil and gas diminished shale gas pressure and resulted in declining gas seepage rates. Our survey documented 12 active western NYS natural gas seeps, whereas >32 seeps have been reported or documented since the 17th century. Preliminary tests showed that SCIAMACHY satellite data did not detect atmospheric methane anomalies over western NYS seeps.

Applicability of micro-FTIR in detecting shale heterogeneity.

Samples of Late Devonian/Early Mississippian New Albany Shale from the Illinois Basin, having maturities ranging from early mature to postmature, were analysed using micro-Fourier transform infrared (FTIR) spectroscopy, ImageJ processing software and scanning electron microscopic X-ray spectroscopy to explore the distribution, connectivity and chemical composition of organic matter, clay minerals, carbonate minerals and quartz, and to further test the applicability of micro-FTIR mapping to study shale heterogeneity. Each sample was analysed in planes parallel and perpendicular to the bedding to investigate anisotropy in component distribution, with a possible implication for better understanding anisotropy in porosity and permeability in organic-matter-rich shales. Our results show that for low-maturity samples, organic matter is better connected in the plane parallel to the bedding than in the plane perpendicular to the bedding. Organic matter connectivity decreases with increasing maturity as a result of kerogen transformation. Clay minerals are very well connected in both planes, whereas carbonate minerals are not abundant whilst dominantly isolated in most samples, independent of maturity. This study demonstrates that micro-FTIR mapping is a valuable tool for studying shale heterogeneity on a micrometre to millimetre scale that becomes even more powerful in combination with scanning electron microscopy techniques, which extend observations to a nanometre scale. However, to obtain meaningful and comparable results, micro-FTIR mapping requires very careful standardization, precise selection of peak heights/areas and mapping conditions (such as aperture size, scan numbers, resolution, etc.) well suited for the analysed samples.

Applications of Micro-Fourier Transform Infrared Spectroscopy (FTIR) in the Geological Sciences--A Review.

Fourier transform infrared spectroscopy (FTIR) can provide crucial information on the molecular structure of organic and inorganic components and has been used extensively for chemical characterization of geological samples in the past few decades. In this paper, recent applications of FTIR in the geological sciences are reviewed. Particularly, its use in the characterization of geochemistry and thermal maturation of organic matter in coal and shale is addressed. These investigations demonstrate that the employment of high-resolution micro-FTIR imaging enables visualization and mapping of the distributions of organic matter and minerals on a micrometer scale in geological samples, and promotes an advanced understanding of heterogeneity of organic rich coal and shale. Additionally, micro-FTIR is particularly suitable for in situ, non-destructive characterization of minute microfossils, small fluid and melt inclusions within crystals, and volatiles in glasses and minerals. This technique can also assist in the chemotaxonomic classification of macrofossils such as plant fossils. These features, barely accessible with other analytical techniques, may provide fundamental information on paleoclimate, depositional environment, and the evolution of geological (e.g., volcanic and magmatic) systems.

Heterogeneity of shale documented by micro-FTIR and image analysis.

In this study, four New Albany Shale Devonian and Mississippian samples, with vitrinite reflectance [Ro ] values ranging from 0.55% to 1.41%, were analyzed by micro-FTIR mapping of chemical and mineralogical properties. One additional postmature shale sample from the Haynesville Shale (Kimmeridgian, Ro = 3.0%) was included to test the limitation of the method for more mature substrates. Relative abundances of organic matter and mineral groups (carbonates, quartz and clays) were mapped across selected microscale regions based on characteristic infrared peaks and demonstrated to be consistent with corresponding bulk compositional percentages. Mapped distributions of organic matter provide information on the organic matter abundance and the connectivity of organic matter within the overall shale matrix. The pervasive distribution of organic matter mapped in the New Albany Shale sample MM4 is in agreement with this shale's high total organic carbon abundance relative to other samples. Mapped interconnectivity of organic matter domains in New Albany Shale samples is excellent in two early mature shale samples having Ro values from 0.55% to 0.65%, then dramatically decreases in a late mature sample having an intermediate Ro of 1.15% and finally increases again in the postmature sample, which has a Ro of 1.41%. Swanson permeabilities, derived from independent mercury intrusion capillary pressure porosimetry measurements, follow the same trend among the four New Albany Shale samples, suggesting that micro-FTIR, in combination with complementary porosimetric techniques, strengthens our understanding of porosity networks. In addition, image processing and analysis software (e.g. ImageJ) have the capability to quantify organic matter and total organic carbon - valuable parameters for highly mature rocks, because they cannot be analyzed by micro-FTIR owing to the weakness of the aliphatic carbon-hydrogen signal.

Geochemistry of ultra-fine and nano-compounds in coal gasification ashes: a synoptic view.

The nano-mineralogy, petrology, and chemistry of coal gasification products have not been studied as extensively as the products of the more widely used pulverized-coal combustion. The solid residues from the gasification of a low- to medium-sulfur, inertinite-rich, volatile A bituminous coal, and a high sulfur, vitrinite-rich, volatile C bituminous coal were investigated. Multifaceted chemical characterization by XRD, Raman spectroscopy, petrology, FE-SEM/EDS, and HR-TEM/SEAD/FFT/EDS provided an in-depth understanding of coal gasification ash-forming processes. The petrology of the residues generally reflected the rank and maceral composition of the feed coals, with the higher rank, high-inertinite coal having anisotropic carbons and inertinite in the residue, and the lower rank coal-derived residue containing isotropic carbons. The feed coal chemistry determines the mineralogy of the non-glass, non-carbon portions of the residues, with the proportions of CaCO3 versus Al2O3 determining the tendency towards the neoformation of anorthite versus mullite, respectively. Electron beam studies showed the presence of a number of potentially hazardous elements in nanoparticles. Some of the neoformed ultra-fine/nano-minerals found in the coal ashes are the same as those commonly associated with oxidation/transformation of sulfides and sulfates.

Dynamic micromapping of CO2 sorption in coal.

We have applied X-ray and neutron small-angle scattering techniques (SAXS, SANS, and USANS) to study the interaction between fluids and porous media in the particular case of subcritical CO2 sorption in coal. These techniques are demonstrated to give unique, pore-size-specific insights into the kinetics of CO2 sorption in a wide range of coal pores (nano to meso) and to provide data that may be used to determine the density of the sorbed CO2. We observed densification of the adsorbed CO2 by a factor up to five compared to the free fluid at the same (p, T) conditions. Our results indicate that details of CO2 sorption into coal pores differ greatly between different coals and depend on the amount of mineral matter dispersed in the coal matrix: a purely organic matrix absorbs more CO2 per unit volume than one containing mineral matter, but mineral matter markedly accelerates the sorption kinetics. Small pores are filled preferentially by the invading CO2 fluid and the apparent diffusion coefficients have been estimated to vary in the range from 5x10(-7) cm2/min to more than 10(-4) cm2/min, depending on the CO2 pressure and location on the sample.

Methane-producing microbial community in a coal bed of the Illinois basin.

A series of molecular and geochemical studies were performed to study microbial, coal bed methane formation in the eastern Illinois Basin. Results suggest that organic matter is biodegraded to simple molecules, such as H(2) and CO(2), which fuel methanogenesis and the generation of large coal bed methane reserves. Small-subunit rRNA analysis of both the in situ microbial community and highly purified, methanogenic enrichments indicated that Methanocorpusculum is the dominant genus. Additionally, we characterized this methanogenic microorganism using scanning electron microscopy and distribution of intact polar cell membrane lipids. Phylogenetic studies of coal water samples helped us develop a model of methanogenic biodegradation of macromolecular coal and coal-derived oil by a complex microbial community. Based on enrichments, phylogenetic analyses, and calculated free energies at in situ subsurface conditions for relevant metabolisms (H(2)-utilizing methanogenesis, acetoclastic methanogenesis, and homoacetogenesis), H(2)-utilizing methanogenesis appears to be the dominant terminal process of biodegradation of coal organic matter at this location.

The investigation of chemical structure of coal macerals via transmitted-light FT-IR microscopy by X. Sun.

A recent paper by Sun [X. Sun, Spectrochim. Acta A 62 (1-3) (2005) 557] attempts to characterize a variety of liptinite, termed "barkinite", from Chinese Permian coals. The component identified does not appear to fundamentally differ from previously-described liptinite macerals included in the International Committee for Coal and Organic Petrology's system of maceral nomenclature. Further, chemical comparisons made with macerals from coals of different rank and age are flawed because the author did not account for changes in chemistry with rank or for the chemical changes associated with botanical changes through geologic time. The author has not satisfactorily proved his hypothesis that the component differs morphologically or chemically from known liptinite-group macerals.

Thermal maturity of type II kerogen from the New Albany Shale assessed by 13C CP/MAS NMR.

Thermal maturity of oil and gas source rocks is typically quantified in terms of vitrinite reflectance, which is based on optical properties of terrestrial woody remains. This study evaluates 13C CP/MAS NMR parameters in kerogen (i.e., the insoluble fraction of organic matter in sediments and sedimentary rocks) as proxies for thermal maturity in marine-derived source rocks where terrestrially derived vitrinite is often absent or sparse. In a suite of samples from the New Albany Shale (Middle Devonian to the Early Mississippian, Illinois Basin) the abundance of aromatic carbon in kerogen determined by 13C CP/MAS NMR correlates linearly well with vitrinite reflectance.