Geology ReportsSearch

USGS · 70017362

An empirical determination of the minimum number of measurements needed to estimate the mean random vitrinite reflectance of disseminated organic matter

Abstract

In coal samples, published recommendations based on statistical methods suggest 100 measurements are needed to estimate the mean random vitrinite reflectance ( R v−r ) to within ±2%. Our survey of published thermal maturation studies indicates that those using dispersed organic matter (DOM) mostly have an objective of acquiring 50 reflectance measurements. This smaller objective size in DOM versus that for coal samples poses a statistical contradiction because the standard deviations of DOM reflectance distributions are typically larger indicating a greater sample size is needed to accurately estimate R v−r in DOM. However, in studies of thermal maturation using DOM, even 50 measurements can be an unrealistic requirement given the small amount of vitrinite often found in such samples. Furthermore, there is generally a reduced need for assuring precision like that needed for coal applications. Therefore, a key question in thermal maturation studies using DOM is how many measurements of R v−r are needed to adequately estimate the mean. Our empirical approach to this problem is to compute the reflectance distribution statistics: mean, standard deviation, skewness, and kurtosis in increments of 10 measurements. This study compares these intermediate computations of R v−r statistics with a final one computed using all measurements for that sample. Vitrinite reflectance was measured on mudstone and sandstone samples taken from borehole M-25 in the Cerro Prieto, Mexico geothermal system which was selected because the rocks have a wide range of thermal maturation and a comparable humic DOM with depth. The results of this study suggest that after only 20–30 measurements the mean R v−r is generally known to within 5% and always to within 12% of the mean R v−r calculated using all of the measured particles. Thus, even in the worst case, the precision after measuring only 20–30 particles is in good agreement with the general precision of one decimal place recommended for mean R v−r measurements on DOM. The coefficient of variation ( V = standard deviation/mean) is proposed as a statistic to indicate the reliability of the mean R v−r estimates made at n ⪡ 20. This preliminary study suggests a V < 0.1 indicates a reliable mean and a V > 0.2 suggests an unreliable mean in such small samples.

Explore related subjects

Keep this discovery

Explore connections, maps & timelines

BibTeXRIS

Charles E. Barker, Mark J. Pawlewicz. 1993. An empirical determination of the minimum number of measurements needed to estimate the mean random vitrinite reflectance of disseminated organic matter. https://doi.org/10.1016/0146-6380(93)90050-l

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