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USGS2005

X-ray scattering and spectroscopy studies on diesel soot from oxygenated fuel under various engine load conditions

Diesel soot from reference diesel fuel and oxygenated fuel under idle and load engine conditions was investigated with X-ray scattering and X-ray carbon K-edge absorption spectroscopy. Up to five characteristic size ranges were found. Idle soot was generally found to have larger primary particles and aggregates but smaller crystallites, than load soot. Load soot has a higher degree of crystallinity than idle soot. Adding oxygenates to diesel fuel enhanced differences in the characteristics of diesel soot, or even reversed them. Aromaticity of idle soot from oxygenated diesel fuel was significantly larger than from the corresponding load soot. Carbon near-edge X-ray absorption fine structure (NEXAFS) spectroscopy was applied to gather information about the presence of relative amounts of carbon double bonds (CC, CO) and carbon single bonds (C-H, C-OH, COOH). Using scanning X-ray transmission microspectroscopy (STXM), the relative amounts of these carbon bond states were shown to vary spatially over distances approximately 50 to 100 nm. The results from the X-ray techniques are supported by thermo-gravimetry analysis and high-resolution transmission electron microscopy. ?? 2005 Elsevier Ltd. All rights reserved.

Carbon↗

USGS2005

Secondary sulfate minerals associated with acid drainage in the eastern US: Recycling of metals and acidity in surficial environments

Weathering of metal-sulfide minerals produces suites of variably soluble efflorescent sulfate salts at a number of localities in the eastern United States. The salts, which are present on mine wastes, tailings piles, and outcrops, include minerals that incorporate heavy metals in solid solution, primarily the highly soluble members of the melanterite, rozenite, epsomite, halotrichite, and copiapite groups. The minerals were identified by a combination of powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and electron-microprobe. Base-metal salts are rare at these localities, and Cu, Zn, and Co are commonly sequestered as solid solutions within Fe- and Fe-Al sulfate minerals. Salt dissolution affects the surface-water chemistry at abandoned mines that exploited the massive sulfide deposits in the Vermont copper belt, the Mineral district of central Virginia, the Copper Basin (Ducktown) mining district of Tennessee, and where sulfide-bearing metamorphic rocks undisturbed by mining are exposed in Great Smoky Mountains National Park in North Carolina and Tennessee. Dissolution experiments on composite salt samples from three minesites and two outcrops of metamorphic rock showed that, in all cases, the pH of the leachates rapidly declined from 6.9 to <3.7, and specific conductance increased gradually over 24 h. Leachates analyzed after 24-h dissolution experiments indicated that all of the salts provided ready sources of dissolved Al (>30 mg L-1), Fe (>47 mg L-1), sulfate (>1000 mg L-1), and base metals (>1000 mg L-1 for minesites, and 2 mg L-1 for other sites). Geochemical modeling of surface waters, mine-waste leachates, and salt leachates using PHREEQC software predicted saturation in the observed ochre minerals, but significant concentration by evaporation would be needed to reach saturation in most of the sulfate salts. Periodic surface-water monitoring at Vermont minesites indicated peak annual metal loads during spring runoff. At the Virginia site, where no winter-long snowpack develops, metal loads were highest during summer months when salts were dissolved periodically by rainstorms following sustained evaporation during dry spells. Despite the relatively humid climate of the eastern United States, where precipitation typically exceeds evaporation, salts form intermittently in open areas, persist in protected areas when temperature and relative humidity are appropriate, and contribute to metal loadings and acidity in surface waters upon dissolution, thereby causing short-term perturbations in water quality.

Chemical Geology↗

USGS2007

Hydrothermal nontronite formation at Eolo Seamount (Aeolian volcanic arc, Tyrrhenian Sea)

A sediment core containing a yellowish-green clay bed was recovered from an area of extensive hydrothermal deposition at the SE slope of the Eolo Seamount, Tyrrhenian Sea. The clay bed is composed of pure nontronite (described for the first time in the Tyrrhenian Sea), which appears to be the most aluminous nontronite ever found among the seafloor hydrothermal deposits. The high Al content suggests precipitation from Al-containing hydrothermal solutions. The REE distribution of the Eolo nontronite has a V-shape pattern. The heavy REE enrichment is in part due to their preferential partitioning in the nontronite structure. This enrichment was possibly further enhanced by the HREE preferential sorption on bacterial cell walls. The light REE enrichment is the result of scavenging uptake by one of the nontronite precursors, i.e., poorly-ordered Fe-oxyhydroxides, from the hydrothermal fluids. Oxygen isotopic composition of the nontronite yields a formation temperature of 30????C, consistent with a low-temperature hydrothermal origin. The relatively radiogenic Nd isotopic signature of the nontronite compared to the present-day Mediterranean seawater indicates that approximately half of Nd, and presumably the rest of the LREE, are derived from local volcanic sources. On the other hand, 87Sr/86Sr is dominated by present-day seawater Sr. Scanning electron microscopy investigation revealed that the nontronite is composed of aggregates of lepispheres and tube-like filaments, which are indicative of bacteria assisted precipitation. Bacteria inhabiting this hydrothermal site likely acted as reactive geochemical surfaces on which poorly-ordered hydrothermal Fe-oxyhydroxides and silica precipitated. Upon aging, the interactions of these primary hydrothermal precipitates coating bacterial filaments and cell walls likely led to the formation of nontronite. Finally, the well-balanced interlayer and layer charges of the crystal lattice of seafloor hydrothermal nontronite decrease its sorption capacity to zero. Thus the ubiquitous nontronite precipitation along the active plate boundaries and around the hot spots has no significant impact on oceanic trace element chemistry. ?? 2007 Elsevier B.V. All rights reserved.

Chemical Geology↗

USGS2008

Mineralogy and geochemistry of a superhigh-organic-sulfur coal, Yanshan Coalfield, Yunnan, China: Evidence for a volcanic ash component and influence by submarine exhalation

The mineralogy and geochemistry of a superhigh-organic-sulfur (SHOS) coal of Late Permian age from the Yanshan Coalfield, Yunnan Province, southwestern China, have been studied using optical microscope, low-temperature ashing plus X-ray diffraction analysis, scanning electron microscope equipped with energy-dispersive X-ray spectrometer, a sequential chemical extraction procedure, and inductively coupled plasma mass spectrometry. The M9 Coal from the Yanshan Coalfield is a SHOS coal that has a total sulfur content of 10.12%-11.30% and an organic sulfur content of 8.77%-10.30%. The minerals in the coal consist mainly of high-temperature quartz, sanidine, albite, muscovite, illite, pyrite, and trace amounts of kaolinite, plagioclase, akermanite, rutile, and dawsonite. As compared with ordinary worldwide (bituminous coals and anthracite) and Chinese coals, the M9 Coal is remarkably enriched in B (268????g/g), F (841????g/g), V (567????g/g), Cr (329????g/g), Ni (73.9????g/g), Mo (204????g/g), and U (153????g/g). In addition, elements including Se (25.2????g/g), Zr (262????g/g), Nb (20.1????g/g), Cd (2.07????g/g), and Tl (2.03????g/g) are also enriched in the coal. Occurrence of high-temperature quartz, sanidine, muscovite, and illite in the M9 Coal is evidence that there is a volcanic ash component in the coal that was derived from acid volcanic ashes fallen into the swamp during peat accumulation. Occurrence of albite and dawsonite in the coal and strong enrichment of some elements, including F, S, V, Cr, Ni, Mo and U, are attributed to the influence by submarine exhalation which invaded along with seawater into the anoxic peat swamp. Abundances of lithophile elements, including rare earth elements, Nb, Y, Zr, and TiO2, indicate that the silicate minerals in the coal were derived from the northern Vietnam Upland to the south of the basin. ?? 2008 Elsevier B.V. All rights reserved.

Chemical Geology↗

USGS2014

Mercury speciation in the Mt. Amiata mining district (Italy): interplay between urban activities and mercury contamination

A fundamental step to evaluate the biogeochemical and eco-toxicological significance of Hg dispersion in the environment is to determine speciation of Hg in solid matrices. In this study, several analytical techniques such as scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), sequential chemical extractions (SCEs), and X-ray absorption spectroscopy (XANES) were used to identify Hg compounds and Hg speciation in samples collected from the Mt. Amiata Hg mining district, southern Tuscany, Italy. Different geological materials, such as mine waste calcine (retorted ore), soil, stream sediment, and stream water suspended particulate matter were analyzed. Results show that the samples were generally composed of highly insoluble Hg compounds such as sulphides (HgS, cinnabar and metacinnabar), and more soluble Hg halides such as those associated with the mosesite group. Other moderately soluble Hg compounds, HgCl 2 , HgO and Hg 0 , were also identified in stream sediments draining the mining area. The presence of these minerals suggests active and continuous runoff of soluble Hg compounds from calcines, where such Hg compounds form during retorting, or later in secondary processes. Specifically, we suggest that, due to the proximity of Hg mines to the urban center of Abbadia San Salvatore, the influence of other anthropogenic activities was a key factor for Hg speciation, resulting in the formation of unusual Hg-minerals such as mosesite.

Tuscany↗

USGS2015

Determination of 1-chloro-4-[2,2,2-trichloro-1-(4-chlorophenyl)ethyl]benzene and related compounds in marine pore water by automated thermal desorption-gas chromatography/mass spectrometry using disposable optical fiber

A method is described for determination of ten DDT-related compounds in marine pore water based on equilibrium solid-phase microextraction (SPME) using commercial polydimethylsiloxane-coated optical fiber with analysis by automated thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS). Thermally cleaned fiber was directly exposed to sediments and allowed to reach equilibrium under static conditions at the in situ field temperature. Following removal, fibers were rinsed, dried and cut into appropriate lengths for storage in leak-tight containers at -20°C. Analysis by TD-GC/MS under full scan (FS) and selected ion monitoring (SIM) modes was then performed. Pore-water method detection limits in FS and SIM modes were estimated at 0.05-2.4ng/L and 0.7-16pg/L, respectively. Precision of the method, including contributions from fiber handling, was less than 10%. Analysis of independently prepared solutions containing eight DDT compounds yielded concentrations that were within 6.9±5.5% and 0.1±14% of the actual concentrations in FS and SIM modes, respectively. The use of optical fiber with automated analysis allows for studies at high temporal and/or spatial resolution as well as for monitoring programs over large spatial and/or long temporal scales with adequate sample replication. This greatly enhances the flexibility of the technique and improves the ability to meet quality control objectives at significantly lower cost.

Journal of Chromatography A↗

USGS2016

Determination of polydimethylsiloxane–water partition coefficients for ten 1-chloro-4-[2,2,2-trichloro-1-(4-chlorophenyl)ethyl]benzene-related compounds and twelve polychlorinated biphenyls using gas chromatography/mass spectrometry

Polymer-water partition coefficients (Kpw) of ten DDT-related compounds were determined in pure water at 25 °C using commercial polydimethylsiloxane-coated optical fiber. Analyte concentrations were measured by thermal desorption-gas chromatography/full scan mass spectrometry (TD–GC/MSFS; fibers) and liquid injection-gas chromatography/selected ion monitoring mass spectrometry (LI–GC/MSSIM; water). Equilibrium was approached from two directions (fiber uptake and depletion) as a means of assessing data concordance. Measured compound-specific log Kpw values ranged from 4.8 to 6.1 with an average difference in log Kpw between the two approaches of 0.05 log units (∼12% of Kpw). Comparison of the experimentally-determined log Kpw values with previously published data confirmed the consistency of the results and the reliability of the method. A second experiment was conducted with the same ten DDT-related compounds and twelve selected PCB (polychlorinated biphenyl) congeners under conditions characteristic of a coastal marine field site (viz., seawater, 11 °C) that is currently under investigation for DDT and PCB contamination. Equilibration at lower temperature and higher ionic strength resulted in an increase in log Kpw for the DDT-related compounds of 0.28–0.49 log units (61–101% of Kpw), depending on the analyte. The increase in Kpw would have the effect of reducing by approximately half the calculated freely dissolved pore-water concentrations (Cfree). This demonstrates the importance of determining partition coefficients under conditions as they exist in the field.

Journal of Chromatography A↗

USGS2005

Mineralogy and geochemistry of a Late Permian coal in the Dafang Coalfield, Guizhou, China: Influence from siliceous and iron-rich calcic hydrothermal fluids

This paper describes the influence of siliceous and iron-rich calcic low-temperature hydrothermal fluids (LTHF) on the mineralogy and geochemistry of the Late Permian No. 11 Coal (anthracitic, Rr =2.85%) in the Dafang Coalfield in northwestern Guizhou Province, China. The No. 11 Coal has high contents of vein ankerite (10.2 vol.%) and vein quartz (11.4 vol.%), with formation temperatures of 85 and 180 ??C, respectively, indicating that vein ankerite and vein quartz were derived from low-temperature calcic and siliceous hydrothermal fluids in two epigenetic episodes. The vein quartz appears to have formed earlier than vein ankerite did, and at least three distinct stages of ankerite formation with different Ca/Sr and Fe/Mn ratios were observed. The two types of mineral veins are sources of different suites of major and trace metals. Scanning electron microscope and sequential extraction studies show that, in addition to Fe, Mg, and Ca, vein ankerite is the dominant source of Mn, Cu, Ni, Pb, and Zn in the coal, and the contents of these five elements are as high as 0.09% and 74.0, 33.6, 185, and 289 ??g/g, respectively. In contrast, vein quartz is the main carrier mineral for platinum-group elements (PGEs) Pd, Pt, and Ir in the coal, and the contents of Pd, Pt, and Ir are 1.57, 0.15, and 0.007 ??g/g, respectively. Sequential extraction showed a high PGE content in the silicate fraction, up to 10.4 ??g/g Pd, 1.23 ??g/g Pt, and 0.05 ??g/g Ir, respectively. It is concluded that the formation of ankerite and quartz and the anomalous enrichment of trace elements in the No. 11 Coal in the Dafang Coalfield, Guizhou, result from the influx of calcic and siliceous low-temperature hydrothermal fluids. ?? 2004 Elsevier B.V. All rights reserved.

International Journal of Coal Geology↗

USGS2006

Petrology and chemistry of Permian coals from the Paraná Basin: 1. Santa Terezinha, Leão-Butiá and Candiota Coalfields, Rio Grande do Sul, Brazil

The current paper presents results on petrological and geochemical coal seam characterization in Permian coal-bearing strata from the Paraná Basin, southern Brazil. Sequence stratigraphic analysis shows that peat accumulation in Permian time was closely linked to transgressive/regressive cycles, with peat accumulation occurring in a predominantly back barrier/lagoonal setting. Coal petrographic analysis indicates subbituminous coals at Candiota and Leão-Butiá and high volatile bituminous coals at Santa Terezinha, where locally the coal seams are thermally altered by volcanic intrusions. Petrographic composition is highly variable, with seams at Candiota and Santa Terezinha frequently enriched in inertinite. Chemical analyses indicate that all coals are mineral matter-rich (mean 49.09 wt.%), with SiO 2 and Al 2 O 3 dominating as determined by ICP-AES. Quartz is also the predominant mineral detected by X-ray diffraction, where it is associated with feldspar, kaolinite and hematite and iron-rich carbonates. The results from Scanning Electron Microscopy are broadly consistent with the bulk chemical and mineralogical analysis. Quartz and clays are common in all samples analyzed. Other minerals observed were, amongst others, carbonates (calcite, siderite, ankerite), pyrite, monazite, kaolinite, barite, sphalerite, rutile and quartz of volcanic origin. The distribution of trace elements is well within the range typical for coal basins of other areas despite the fact that the Paraná Basin coals are very high in ash yields. The average concentrations for elements of environmental concern (As, B, Be, Cd, Co, Cr, Cu, Hg, Li, Mn, Mo, Ni, Pb, Sb, Se, Tl, U, V, Zn) are similar to or less than the mean values for U.S. coal. However, considered on an equal energy basis, Paraná Basin coals will produce in combustion 5 to 10 times the amount of most elements compared to an equal weight US coal. Concentrations of major and trace elements, such as Fe, B and S, appear to be controlled by depositional setting, with increasing values in coal seams overlain by brackish/marine strata. Hierarchical cluster analysis identified three groups of major minerals and seven groups of trace elements based on similarity levels. On a regional scale, the coalfields can be separated by the differences in rank (Candiota and Leão-Butiá versus Santa Terezinha) and by applying discriminant analysis based on 4 trace elements (Li, As, Sr, Sb). Highest Rb and Sr values occur at Candiota and are linked to syngenetic volcanism of the area, whereas high Y and Sr values at Santa Terezinha can be related to the frequent diabase intrusions in that area.

International Journal of Coal Geology↗

USGS2008

Mineralogical and compositional characteristics of Late Permian coals from an area of high lung cancer rate in Xuan Wei, Yunnan, China: Occurrence and origin of quartz and chamosite

Some townships in Xuan Wei County, Yunnan Province, have one of the highest lung cancer mortality rates in China and the epidemic disease in the area has generally been attributed to the polycyclic aromatic hydrocarbons (PAHs) released from domestic coal burning. However, the cancer-causing culprit is not settled as Tian [Tian, L., 2005. Coal Combustion Emissions and Lung Cancer in Xuan Wei, China. Ph.D. thesis, University of California, Berkeley.] found nanometer quartz in these coals, soot emissions, and lung cancer tissues. We have conducted mineralogical and geochemical studies of the coals from Xuan Wei for the purpose of shedding light on the minerals which may be related to the epidemic lung cancer. In this paper, abundances, modes of occurrence, and origins of minerals and elements in the coals from two mines in Xuan Wei have been studied using optical microscope, low-temperature ashing, X-ray diffraction analysis, scanning electron microscope equipped with energy-dispersive X-ray spectrometer, and inductively-coupled plasma mass spectrometry. The minerals in the coals are mainly composed of quartz, chamosite, kaolinite, and calcite. The particle size of quartz is rather small, mostly less than 20????m and it is of authigenic origin. Chamosite occurs mainly as cell-fillings. The occurrence of quartz and chamosite indicates that they were derived from the hydrothermal fluids. Epigenetic calcite is derived from calcic fluids. Kaolinite is derived mainly from sediment source region of Kangdian Oldland to the west of coal basin. The composition of Xuan Wei coal is high in SiO2, Fe2O3, TiO2, CaO, MnO, V, Co, Ni, Cu, and Zn. The high SiO2 content is attributed to quartz, and the Fe2O3 content to chamosite. The high Mn and low Mg contents in the coal indicate the inputs of hydrothermal fluids. CaO occurs mainly in epigenetic calcite. Elements Ti, Co, Ni, Cu, Zn, and rare earth elements were derived from the basaltic rocks at sediment source region. ?? 2008 Elsevier B.V. All rights reserved.

International Journal of Coal Geology↗

USGS2010

A high-pyrite semianthracite of Late Permian age in the Songzao Coalfield, southwestern China: Mineralogical and geochemical relations with underlying mafic tuffs

The No. 12 Coal (Late Permian) in the Songzao Coalfield, Chongqing, southwestern China, is characteristically high in pyrite and some trace elements. It is uniquely deposited directly above mafic tuff beds. Samples of coal and tuffs have been studied for their mineralogy and geochemistry using inductively coupled plasma-mass spectrometry, X-ray fluorescence, plasma low-temperature ashing plus powder X-ray diffraction, and scanning electron microscopy equipped with energy-dispersive X-ray analysis.The results show that the minerals of the No. 12 Coal are mainly composed of pyrite, clay minerals (kaolinite, chamosite, and illite), ankerite, calcite, and trace amounts of quartz and boehmite. Kaolinite and boehmite were mainly derived from sediment source region of mafic tuffs. Chamosite was formed by the reaction of kaolinite with Fe-Mg-rich fluids during early diagenesis. The high pyrite (Sp,d=8.83%) in the coal was related to marine transgression over peat deposits and abundant Fe derived from the underlying mafic tuff bed. Ankerite and calcite were precipitated from epigenetic fluids.Chemical compositions of incompatible elements indicate that the tuffs were derived from enriched mantle and the source magmas had an alkali-basalt character. Compared to other coals from the Songzao Coalfield and common Chinese coals, the No. 12 Coal has a lower SiO2/Al2O3 (1.13) but a higher Al2O3/Na2O (80.1) value and is significantly enriched in trace elements including Sc (13.5??g/g), V (121??g/g), Cr (33.6??g/g), Co (27.2??g/g), Ni (83.5??g/g), Cu (48.5??g/g), Ga (17.3??g/g), Y (68.3??g/g), Zr (444??g/g), Nb (23.8??g/g), and REE (392??g/g on average). Above mineralogical compositions, as well as similar ratios of selected elements (e.g., SiO2/Al2O3 and Al2O3/Na2O) and similar distribution patterns of incompatible elements (e.g., the mantle-normalized diagram for incompatible elements and chondrite-normalized diagram for rare earth elements) of coal and tuff, indicated that enriched trace elements above were largely derived from mafic tuffs, in addition to a minor amount from the Kandian Oldland. ?? 2010 Elsevier B.V.

International Journal of Coal Geology↗

USGS2018

Pore-types and pore-network evolution in Upper Devonian-Lower Mississippian Woodford and Mississippian Barnett mudstones: Insights from laboratory thermal maturation and organic petrology

Pore-evolution models from immature organic-matter (OM) -rich Barnett (0.42%R o ) and Woodford (0.49%R o ) mudstones were compared with models previously developed from low-maturity OM-lean Boquillas (Eagle Ford-equivalent) mudstones to investigate whether (1) different mineralogy (siliceous vs. calcareous) exerts different catalytic and sorption effects and influences OM-pore origin and evolution; and (2) different types of macerals show different OM pore evolution history. Laboratory gold-tube pyrolysis, scanning electron microscopy (SEM) and thin-section petrography, organic petrography, and geochemical characterization were used to investigate the role of bulk mineralogy, maceral type, and thermal maturation on OM-pore evolution. Results suggest that mineralogy has little impact on OM-pore development and evolution. Macerals, identified using both SEM (platy OM, particulate OM, organic–mineral admixtures, Tasmanites ) and organic petrology (vitrinite, inertinite, amorphous organic matter [AOM]/bituminite, telalginite [ Leiosphaeridia , Tasmanites ]), do affect the origin and evolution of OM pores owing to differences in chemical compositions, generation kinetics, and activation-energy distributions between Tasmanites , matrix bituminite, and other types of macerals. Leiosphaeridia and Tasmanites in Woodford mudstone samples exhibit a delay in onset and a shorter period of petroleum generation and pore development compared to the matrix bituminite in the Barnett and Woodford mudstone samples. Pre-oil solid bitumen was observed to have migrated into initial primary mineral pore networks at the bitumen generation stage in both Barnett and Woodford samples. At higher levels of thermal maturation, the volume of primary mineral pores decreases and the pore volume composed of modified mineral pores and OM pores becomes greater. Pore evolution and pore-type heterogeneity in these mudstones is a function of the initial mineral pore network, types of kerogen and macerals, and generation kinetics of individual macerals upon thermal maturation.

Oklahoma↗

USGS2019

Application of electron microscopy TEM and SEM for analysis of coals, organic-rich shales and carbonaceous matter

This paper provides a brief summary of the history, development and variety of applications of electron microscopy techniques to analyze coals, organic-rich shales, and carbonaceous materials. General construction and principles of operation of transmitted (TEM) and scanning electron microscope (SEM) are outlined, along with guidance on specimen preparation, and a brief overview of published TEM and SEM applications related to coal, shales, and carbonaceous materials. This work was accepted as the chapter 18.2 of International Committee for Coal and Organic Petrology Methods Handbook at the ICCP Plenary Session on September 27, 2018 in Brisbane (Australia).

International Journal of Coal Geology↗

USGS2022

Evaluating aromatization of solid bitumen generated in the presence and absence of water: Implications for solid bitumen reflectance as a thermal proxy

Geological models for petroleum generation suggest thermal conversion of oil-prone sedimentary organic matter in the presence of water promotes increased liquid saturate yield, whereas absence of water causes formation of an aromatic, cross-linked solid bitumen residue. To test the influence of hydrogen from water, organic-rich (22 wt% total organic carbon , TOC) mudrock samples from the Eocene lacustrine Green River Formation Mahogany zone oil shale were pyrolyzed under hydrous and anhydrous conditions in closed system batch reactors at temperatures between 300 and 370 °C for 72 h. Pre- and post-pyrolysis samples were characterized using petrographic approaches including optical microscopy , reflectance, Raman spectroscopy , and scanning electron and transmission electron microscopy to quantify differences in relative appearance, abundance, and composition of solid bitumen newly generated during the pyrolysis experiments. Petrographic analyses were supplemented by geochemical screening measurements (TOC content and programmed temperature pyrolysis). Results show post-hydrous pyrolysis residues contain lower TOC, are comprised of solid bitumen with greater aromaticity , and have textures indicative of lower viscosities, relative to anhydrous residues from the same temperature pyrolysis conditions. These observations suggest solid bitumen forming from thermal conversion of oil-prone sedimentary organic matter under anhydrous conditions may be less aromatic, although more cross-linked, than solid bitumen forming under hydrous conditions at the same time-temperature combination. To explain these results, we suggest that a radical disproportionation mechanism is favored in the presence of hydrogen donated from water, and that this disproportionation promotes aromatization in the solid residue with concomitant expulsion of saturated hydrocarbons.

International Journal of Coal Geology↗

USGS2025

Relating systematic molecular and textural properties of graptolite pyrolyzed via gold tube hydrous pyrolysis: Implications for thermal proxies in lower Paleozoic marine shales

A series of gold tube pyrolysis experiments (72 h, 300–550 °C, 50 MPa) conducted on a graptolite-rich lower Paleozoic marine shale generated pyrolysis residues for a comprehensive evaluation of the molecular and structural variability of three types of graptolite periderm. Organic petrology, Raman spectroscopy, and field emission scanning electron microscopy (FE-SEM) with energy dispersive spectroscopy (EDS) were combined to evaluate the thermal evolution process. The three types of graptolite periderm, namely granular, non-granular, and nodular graptolite, were analyzed by Raman spectroscopy wherein point measurements were obtained after the maceral was identified and the location verified by organic petrology. Distinct thermal evolution pathways among non-granular, granular, and nodular graptolite periderms were recorded. The evolution patterns of the Raman parameters, particularly D1 and G bands, highlight the differences in geochemical composition of the graptolite periderm types and the alteration of molecular structure with increasing thermal maturity. Raman parameters D1 (position of the D1 peak), G-FWHM (full width at half maximum of the G peak), and ratios D1-FWHM/G-FWHM (full width at half maximum of the D1 peak ratioed to G-FWHM) and A D1 /A G (ratio of D1 and G peak intensities) showed effectiveness in assessing thermal maturity. Bireflectance with increasing gold tube pyrolysis temperature followed a hierarchy: non-granular > granular > nodular, reflecting different molecular alignment intensities. Qualitative FE-SEM evaluation showed that fine-grained mineral inclusions (primarily Fe-sulfide as determined via EDS) were associated with the graptolite populations, with granular graptolite containing greater amounts of coarser-grained (e.g., ∼300–1400 nm) mineral inclusions relative to non-granular and nodular graptolite, which contain finer-grained (e.g., ∼100–200 nm) inclusions difficult to resolve with optical microscopy. These findings are investigated to highlight the mechanisms that drive organic matter evolution within graptolite during thermal maturation, as well as to explore some of the limitations of using spectroscopic parameters as thermal maturity proxies.

International Journal of Coal Geology↗

USGS2023

Remotely sensed short-crested breaking waves in a laboratory directional wave basin

Short-crested breaking waves that result from directionally spread wave conditions dissipate energy and generate turbulence within the surf zone, altering sediment transport processes, wave runup, and forces on structures. Additionally, vertical vorticity generated near crest ends during breaking, which depends on the gradient in wave height along a crest, may enhance nearshore dispersion of pollutants, nutrients, and larvae. Although directionally spread irregular wave fields are ubiquitous on ocean and large lake coastlines, the dependence of short-crested breaking wave characteristics (including the along-crest length and number of crest ends) on offshore wave conditions is not well established. To assess this relationship, laboratory experiments with alongshore-uniform barred bathymetry were performed in a large-scale directional wave basin. A three-dimensional scanning lidar, trinocular camera stereo processing methods, and in situ measurements were used to study short-crested wave field breaking characteristics in the laboratory, yielding a dataset with dense spatio-temporal coverage relative to prior laboratory or field measurements. Wave height estimates are similar for remotely sensed and in situ observations, except in the outer surf zone where plunging breaking occurred. Directional wave properties estimated with an array of in situ or remotely sensed sea-surface elevation estimates are similar and yield smaller directional spreads than single-point colocated pressure and velocity based in situ estimates when waves are less directionally spread. Using a breaking crest identification procedure combining visible imagery and stereo sea-surface elevation, we find that the average along-crest length of breaking waves decreases and the average number of crest ends increases with increasing directional spread. Relative to observations, a parameterized relationship between directional spread and crest characteristics based on theory for non-breaking, refracting waves generally over-estimates breaking crest lengths and is similar to or underestimates the total number of crest ends observed in the surf zone. The wave-field-dependent breaking-wave characteristics examined in the laboratory with remote sensing techniques can inform future investigations of depth-limited short-crested wave breaking and resulting surfzone eddy processes.

Coastal Engineering↗

USGS2008

Time-averaged near-bed suspended sediment concentrations under waves and currents: Comparison of measured and model estimates

Profiles of suspended sediment concentration and velocity were measured over a 15-day period at a near-shore site off Santa Cruz, CA in Monterey Bay. The concentration and velocity data were collected with an Acoustic Backscattering System (ABS) and Acoustic Current Profiler (ACP) that were mounted on a bottom tripod. High-resolution bottom scanning sonar was also attached to the tripod to provide images of bed features during the experiment. Hourly time-averaged near-bed concentrations of suspended sediment were calculated from three models and compared with the measurements. Surface waves and currents that were generated by a storm of moderate intensity caused bed stresses that exceeded threshold stress for D 50 =0.02 cm, the median size of the moderately well-sorted bottom sediment, over a period of about 7 days. Estimates of the concentration at 1 cm above the bottom, C a1 , were obtained using the ABS measurements. These observations have been compared with predictions for the concentration at 1 cm above the bottom, C 1 . Nielsen's models for reference concentration C o [Nielsen, P., 1986. Suspended sediment concentrations under waves. Coastal Engineering 10, 32-31; Nielsen, P., 1992. Coastal Bottom Boundary Layers and Sediment Transport, Advanced Series on Ocean Engineering. World Scientific, Hackensack, NJ.] are purely wave-based and do not include effects of bottom currents on bed stress and bedform scales. C 1 calculated from this model compared well with measured C a1 when currents were weak and small oscillatory ripples were observed in the sonar images. However, during the 3-day period of highest bottom stresses modeled C 1 did not compare well to C a1 . The other two models for C 1 , Glenn and Grant [Glenn, S.M., Grant, W.D., 1987. A suspended sediment stratification correction for combined wave and current flows. Journal of Geophysical Research 92(C8), 8244-8264.] and van Rijn and Walstra [Van Rijn, L.C., Walstra, D.J.R., 2004. Description of TRANSPOR2004 and implementation in Delft3D-ONLINE. Interim Report prepared for DG Rijkswaterstaat, Rijksinstituut voor Kust en Zee. Delft Hydraulics Institute, The Netherlands.], accounted for combined wave-current stresses and included different formulations for predicting bedform scales. C 1 calculated from these models compared well with measurements throughout the early and middle period of the storm, but underpredicted measured values during the latter part of the experiment. An alternative method based on dimensional analysis provided a straightforward way to relate C 1 to bed stress and sediment parameters. This new relationship based on dimensional analysis explained about 77% of the variability in C a1 derived from the ABS data.

California↗

USGS2016

Geology and biology of the "Sticky Grounds," shelf-margin carbonate mounds, and mesophotic ecosystem in the eastern Gulf of Mexico

Shelf-margin carbonate mounds in water depths of 116–135 m in the eastern Gulf of Mexico along the central west Florida shelf were investigated using swath bathymetry, side-scan sonar, sub-bottom imaging, rock dredging, and submersible dives. These enigmatic structures, known to fisherman as the “Sticky Grounds”, trend along slope, are 5–15 m in relief with base diameters of 5–30 m, and suggest widespread potential for mesophotic reef habitat along the west Florida outer continental shelf. Possible origins are sea-level lowstand coral patch reefs, oyster reefs, or perhaps more recent post-lowstand biohermal development. Rock dredging recovered bioeroded carbonate-rock facies comprised of bored and cemented bioclastics. Rock sample components included calcified worm tubes, pelagic sediment, and oysters normally restricted to brackish nearshore areas. Several reef sites were surveyed at the Sticky Grounds during a cruise in August 2010 with the R/V Seward Johnson using the Johnson-Sea-Link II submersible to ground truth the swath-sonar maps and to quantify and characterize the benthic habitats, benthic macrofauna, fish populations, and coral/sponge cover. This study characterizes for the first time this mesophotic reef ecosystem and associated fish populations, and analyzes the interrelationships of the fish assemblages, benthic habitats and invertebrate biota. These highly eroded rock mounds provide extensive hard-bottom habitat for reef invertebrate species as well as essential fish habitat for reef fish and commercially/recreationally important fish species. The extent and significance of associated living resources with these bottom types is particularly important in light of the 2010 Deepwater Horizon oil spill in the northeastern Gulf and the proximity of the Loop Current. Mapping the distribution of these mesophotic-depth ecosystems is important for quantifying essential fish habitat and describing benthic resources. These activities can improve ecosystem management and planning of future oil and gas activities in this outer continental shelf region.

Continental Shelf Research↗