USGS Science⌕ Search

USGS · 70018026

Relationships between data from Rock-Eval pyrolysis and proximate, ultimate, petrographic, and physical analyses of 142 diverse U.S. coal samples

Abstract

Basic research on coal and oil shale led to automated pyrolysis analysis of petroleum source rocks; most widely used is the Rock-Eval equipment. In order to interpret Rock-Eval analyses in relation to traditional coal data, we analyzed 142 commercial coals with diverse rank, age, maceral and sulfur contents, for most regions of the United States. We compared the Rock-Eval data with traditional industrial coal data, including volatile matter, calorific value, hydrogen and oxygen content, free swelling index, and vitrinite reflectance. We found: (1) there is a close relationship between T max and vitrinite reflectance in the ranges 420–590°C T max and 0.4–3% R o max of most coals. (2) A close relationship between T max and volatile matter (%VM) extends through the entire sample range, including low-rank samples with 35–70% VM, a range where %VM is not considered to be a useful rank parameter. (3) TOC of medium- and high-rank coals is seriously under-measured by Rock-Eval; TOC of low-rank coals (less than 0.8% R o max ) is close to “dry basis” carbon from ultimate analysis. (4) The direct relationships between oxygen index (OI) and %O and between hydrogen index (HI) and %H are clear, though only broadly defined. However, there is virtually no band of concentrated data points on the HI versus OI pseudo-Van Krevelen diagram comparable to the “development line” on the H/C versus O/C diagram. (5) There are systematic relationships between Rock-Eval and industrial coal parameters such as calorific value and FSI, but much standardization would be needed before Rock-Eval could find a place in the coal industry. Tests with blends of coal and quartz sand and with various loads of coal alone showed that the amount of organic matter in the Rock-Eval load greatly influences results. Total load in the crucible, if largely inert, plays a small role, however. Increasing absolute or relative coal content causes under-evaluation of Rock-Eval TOC and over-rating of hydrogen. Blends of several coals yielded hydrogen and oxygen indexes related proportionally to the properties of the individual coals, but T max is not raised by addition of high-rank coal until over 40% is added.

Explore related subjects

Keep this discovery

Explore connections, maps & timelines

BibTeXRIS

Neely Bostick, Ted A. Daws. 1994. Relationships between data from Rock-Eval pyrolysis and proximate, ultimate, petrographic, and physical analyses of 142 diverse U.S. coal samples. https://doi.org/10.1016/0146-6380(94)90086-8

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related USGS reports

Evidence for a biological origin of uranium-rich carbon masses within the Ediacaran Salt Range Formation of Pakistan

Thucholites are unique organic structures found in igneous and sedimentary rocks composed of a U-C-rich interior enclosed by an organic outer shell. Their formation and occurrence have perplexed scientists for over 100 years. Typically, thucholites are sparse in sedimentary rocks but where found in abundance, they may be the result of rapid paleoecological disruptions, e.g., volcanic ashfall. Here, we evaluated thucholites from the Ediacaran Salt Range Formation of the Indus Basin in Pakistan using field emission scanning electron microscopy (FESEM) and nanoscale secondary ion mass spectroscopy (NanoSIMS) to propose a two-stage mechanism for thucholite development. NanoSIMS results suggest organic matter in thucholite cores formed by biological fractionation (represented by the presence of lighter 13 C/ 12 C and 34 S/ 32 S) while the outer organic mantle formed via radiolysis-induced polymerization. FESEM elemental analysis confirms compositional differences between the two thucholite components (core and mantle), further implying their contrasting origins. Dimensional comparison of thucholite cores and their U-bearing mineral morphologies to ancient and modern U-biomineralized microbes suggests that the thucholite cores formed from metal-biological interactions. The presence of volcanogenic biotite, alkali feldspar, and clay spherules (interpreted as devitrified volcanic glass) with thucholite suggests that the thucholite cores in the Salt Range Formation are biological responses to rapid paleoenvironmental change from volcanic eruption which preserved the fossilized morphologies of Proterozoic microorganisms.

Salt Range↗

Metalloporphyrins in the Eagle Ford Shale

Using Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), Zheng et al. (2018, Energy & Fuels 32, 10382) reported abundant iron and vanadyl porphyrins and minor amounts of gallium and nickel porphyrins in asphaltenes extracted from a single lower Eagle Ford Shale sample. This finding is most unusual as iron and gallium porphyrins have been previously found only in coal. In this study, petroporphyrins in samples of the Eagle Ford Shale previously studied by French et al. (2020, Marine Petrol. Geol. 118, 104459), were examined using atmospheric pressure photoionization (APPI) FT-ICR-MS. Vanadyl porphyrins (N4VO) dominated the asphaltenes in thermally immature (VRo < 0.56%) samples decreasing in relative abundance with increasing maturity. Only minor amounts of nickel porphyrins were detected in the immature and early oil samples. The distribution of the vanadyl porphyrins is comparable to those reported for marine oils at varying levels of maturity. Immature samples contained porphyrins that were predominantly deoxophylloerythroetio- (DPEP: DBE = 18) and di- deoxophylloerythroetio (di-DPEP: DBE = 19) porphyrins, while ETIO- (DBE = 17), rhodo- (DBE = 20, 21, and 22) and higher condensed (DBE ≥ 23) porphyrins increased with increasing maturity. The vanadyl porphyrins included species with additional one to three oxygen atoms (N4VOx, x= 1 to 4) and one sulfur atom with one to two oxygen atoms (S1N4VOx, x=1 to 3). The degree of additional oxygen and sulfur atoms is consistent with O/C and Sorg/C of associated kerogen. No iron or gallium porphyrins were detected, showing that they are not a ubiquitous feature of the Eagle Ford. We hypothesize that the previously reported iron and gallium porphyrins (Zheng et al., 2018) were present because the specific sample that was analyzed in detail was from the early onset of the Cenomanian–Turonian oceanic anoxic event (OAE-2) in contrast to the samples investigated in this study that are primarily from the lower part of the Eagle Ford pre-dating OAE-2. Submarine volcanism, associated with eruption of large igneous provinces, occurred pre-OAE-2, injecting iron and other inorganic nutrients, giving rise to algal blooms and the acidification of the seawater. At the onset of OAE-2, boreal water masses flowed into the southern Western Interior Seaway, shifting the water column to more oxygenated conditions. Low pH-high Eh (oxic) conditions enhance the availability of iron and gallium such that these events abruptly changed the seawater chemistry, specifically enriching iron and gallium relative to vanadium and nickel. These pH-Eh conditions are similar to the depositional conditions associated with coals, which are known to contain iron and gallium porphyrins, suggesting similar conditions resulted in iron and gallium metalation of porphyrins in the marine setting of the Western Interior Seaway.

Texas↗

Validation of the U37K' paleotemperature proxy in the South Brazilian Bight from core-top sediments

The paleothermometer based on the alkenone unsaturation index ( U 37 K &#x2032; "> U37K′ ) is often used to reconstruct past sea surface temperatures (SST). In the SW Atlantic Ocean, however, a limited understanding of the seasonal and depth distribution of coccolithophores, which generates the U 37 K &#x2032; "> U37K′ signal preserved in ocean sediments, hinders accurate estimates of past regional SSTs. We analyzed 45 core-top sediment samples from the continental shelf of the South Brazilian Bight (SBB, 23 °S to 28 °S) to assess regional spatial U 37 K &#x2032; "> U37K′ -SST gradients and improve SST estimates. The U 37 K &#x2032; "> U37K′ data were converted to SST using six published paleotemperature equations and compared to modern observational SST data from the World Ocean Atlas (2018) data set. Data indicate that the U 37 K &#x2032; "> U37K′ signal is produced during the austral summer and autumn when regional episodic upwelling events occur over the inner-shelf and the nutricline shoals at the slope. Our analysis of core-top data shows that SST estimates derived from most calibration equations closely align with modern observed temperatures but are skewed toward warmer months associated with upwelling-derived nutrients. Our findings underscore the importance of considering regional and seasonal biases to improve the accuracy of paleotemperature reconstructions. Understanding the factors influencing the SBB U 37 K &#x2032; "> U37K′ signal enables a more meaningful comparison between regional paleoceanographic studies, improving our understanding of past changes in the SW Atlantic Ocean and our ability to predict regional SST response to ongoing and future warming.

South Brazilian Bight↗