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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

Monitoring gas and heat emissions at Norris Geyser Basin, Yellowstone National Park, USA based on a combined eddy covariance and Multi-GAS approach

We quantified gas and heat emissions in an acid-sulfate, vapor-dominated area (0.04-km 2 ) of Norris Geyser Basin, located just north of the 0.63 Ma Yellowstone Caldera and near an area of anomalous uplift. From 14 May to 3 October 2016, an eddy covariance system measured half-hourly CO 2 , H 2 O and sensible ( H ) and latent ( LE ) heat fluxes and a Multi-GAS instrument measured (1 Hz frequency) atmospheric H 2 O, CO 2 and H 2 S volumetric mixing ratios. We also measured soil CO 2 fluxes using the accumulation chamber method and temperature profiles on a grid and collected fumarole gas samples for geochemical analysis. Eddy covariance CO 2 fluxes ranged from − 56 to 885 g m − 2 d − 1 . Using wavelet analysis, average daily eddy covariance CO 2 fluxes were locally correlated with average daily environmental parameters on several-day to monthly time scales. Estimates of CO 2 emission rate from the study area ranged from 8.6 t d − 1 based on eddy covariance measurements to 9.8 t d − 1 based on accumulation chamber measurements. Eddy covariance water vapor fluxes ranged from 1178 to 24,600 g m − 2 d − 1 . Nighttime H and LE were considered representative of hydrothermal heat fluxes and ranged from 4 to 183 and 38 to 504 W m − 2 , respectively. The total hydrothermal heat emission rate ( H + LE + radiant) estimated for the study area was 11.6 MW and LE contributed 69% of the output. The mean ± standard deviation of H 2 O, CO 2 and H 2 S mixing ratios measured by the Multi-GAS system were 9.3 ± 3.1 parts per thousand, 467 ± 61 ppmv, and 0.5 ± 0.6 ppmv, respectively, and variations in the gas compositions were strongly correlated with diurnal variations in environmental parameters (wind speed and direction, atmospheric temperature). After removing ambient H 2 O and CO 2 , the observed variations in the Multi-GAS data could be explained by the mixing of relatively H 2 O-CO 2 -H 2 S-rich fumarole gases with CO 2 -rich and H 2 O-H 2 S-poor soil gases. The fumarole H 2 O/CO 2 and CO 2 /H 2 S end member ratios (101.7 and 27.1, respectively, on average) were invariant during the measurement period and fell within the range of values measured in direct fumarole gas samples. The soil gas H 2 O/CO 2 end member ratios (~ 15–30) were variable and low relative to the fumarole end member, likely resulting from water vapor loss during cooling and condensation in the shallow subsurface, whereas the CO 2 /H 2 S end member ratio was high (~ 160), presumably related to transport of CO 2 -dominated soil gas emissions mixed with trace fumarolic emissions to the Multi-GAS station. Nighttime eddy covariance ratios of H 2 O to CO 2 flux were typically between the soil gas and fumarole end member H 2 O/CO 2 ratios defined by Multi-GAS measurements. Overall, the combined eddy covariance and Multi-GAS approach provides a powerful tool for quasi-continuous measurements of gas and heat emissions for improved volcano-hydrothermal monitoring.

Wyoming

Coal compositional changes along a mire interior to mire margin transect in the Mary Lee coal bed, Warrior Basin, Alabama, USA

Vertical increment samples of the Mary Lee coal bed, collected along an inferred mire interior to mire margin transect, were studied palynologically, petrographically and geochemically to determine if any vertical or lateral changes in coal composition could be detected. Results show the Mary Lee palynoflora to be dominated by Lycospora spp. (arboreous lycophytes), with other lycophyte genera, Crassispora (Sigillaria) and Densosporites (small lycophytes), occurring less frequently. Commonly encountered fern/pteridosperm miospore genera include Leiotriletes, Granulatisporites, Lophotriletes and Schulzospora . Calamospora , representing calamites, and Florinites , representing cordaites, are minor constituents of the overall palynoflora. Petrographically, the Mary Lee coal bed contains high percentages (> 75% mineral matter free, mmf) of vitrinite macerals, with cryptotelinite being by far the most common type. Cryptogelocollinite is the second most abundant vitrinite maceral. Inertinite maceral percentages are variable, ranging from 8% to 30% (mmf) and liptinite macerals are a relatively minor constituent of the Mary Lee coal bed (3–8% mmf). Both vertical and lateral changes in coal composition occur along the transect studied. Lateral changes include an increase in ash yield and sulfur content from the interior to margin; for example, the average ash yield and sulfur content at location 073 (most interior) are 13.7% and 0.55%, respectively, whereas at location 083 (most marginal) the average ash and sulfur values (calculated from coal increments only) are 32.3% and 3.62%, respectively. Palynofloral changes, from the interior to margin, include a general increase in Lycospora pusilla (Lepidodendron) over Lycospora pellucida (Lepidophloios) and an increase in fern and calamite spores and cordaite pollen. An increase in poorly preserved miospore assemblages was also observed in this direction. At locations 016 and 026, coal increments between the lower and middle partings were barren of palynomorphs, except for one increment in column 016. Petrographically, these increments were completely (> 95% mmf) dominated by cryptotelinite; both liptinite and inertinite macerals were conspicuously absent. In contrast, increments above the middle partings at these locations contained elevated percentages of inertinite macerals, relative to more interior locations. Vertical changes were also noted. At mire interior locations, basal coal layers contain either an arboreous lycophyte-dominant assemblage, with abundant Lycospora pusilla , or a lycophyte-fern/pteridosperm co-dominant assemblage. This palynoflora grades upward into a Lycospora pellucida, L. granula -dominant palynoflora in the middle layers and ultimately into a palynoflora containing an abundant fern/pteridosperm element. Petrographically, the coal at these locations is dominated overall by cryptotelinite, with an increase in inertinite occurring in the uppermost increments. The overall dominance of arboreous lycophytes and cryptotelinite in the Mary Lee coal bed suggests that the Mary Lee paleomire developed under predominantly wet conditions. The moderate (at interior locations) to high (at marginal locations) ash yield of the coal further suggests that the mire developed under planar to near-planar conditions.

International Journal of Coal Geology

Depositional setting, petrology and chemistry of Permian coals from the Paraná Basin: 2. South Santa Catarina Coalfield, Brazil

In Brazil economically important coal deposits occur in the southern part of the Paraná Basin, where coal seams occur in the Permian Rio Bonito Formation, with major coal development in the states of Rio Grande de Sul and Santa Catarina. The current paper presents results on sequence stratigraphic interpretation of the coal-bearing strata , and petrological and geochemical coal seam characterization from the South Santa Catarina Coalfield, Paraná Basin. In terms of sequence stratigraphic interpretation the precursor mires of the Santa Catarina coal seams formed in an estuarine-barrier shoreface depositional environment , with major peat accumulation in a high stand systems tract (Pre-Bonito and Bonito seams), a lowstand systems tract (Ponta Alta seam, seam A, seam B) and a transgressive systems tract (Irapuá, Barro Branco and Treviso seams). Seam thicknesses range from 1.70 to 2.39 m, but high proportions of impure coal (coaly shale and shaley coal), carbonaceous shale and partings reduce the net coal thickness significantly. Coal lithoypes are variable, with banded coal predominant in the Barro Branco seam, and banded dull and dull coal predominantly in Bonito and Irapuá seams, respectively. Results from petrographic analyses indicate a vitrinite reflectance range from 0.76 to 1.63 %Rrandom (HVB A to LVB coal). Maceral group distribution varies significantly, with the Barro Branco seam having the highest vitrinite content (mean 67.5 vol%), whereas the Irapuá seam has the highest inertinite content (33.8 vol%). Liptinite mean values range from 7.8 vol% (Barro Branco seam) to 22.5 vol% (Irapuá seam). Results from proximate analyses indicate for the three seams high ash yields (50.2 – 64.2 wt.%). Considering the International Classification of in-Seam Coals, all samples are in fact classified as carbonaceous rocks (> 50 wt.% ash). Sulfur contents range from 3.4 to 7.7 wt.%, of which the major part occurs as pyritic sulfur. Results of X-ray diffraction indicate the predominance of quartz and kaolinite (also pyrite). Gypsum , gibbsite , jarosite and calcite were also identified in some samples. Feldspar was noted but is rare. The major element distribution in the three seams (coal basis) is dominated by SiO 2 (31.3 wt.%, mean value), Al 2 O 3 (14.5 wt.%, mean value) and Fe 2 O 3 (6.9 wt.%, mean value). Considering the concentrations of trace elements that are of potential environmental hazards the Barro Branco, Bonito and Irapuá seams (coal base) are significantly enriched in Co (15.7 ppm), Cr (54.5 ppm), Li (59.3 ppm), Mn (150.4 ppm), Pb (58.0 ppm) and V (99.6 ppm), when compared to average trace elements contents reported for U. S. coals. Hierarchical cluster analysis identified, based on similarity levels, three groups of major elements and seven groups of trace elements. Applying discriminant analyses using trace and major element distribution, it could be demonstrated that the three seams from Santa Catarina show distinct populations in the discriminant analyses plots, and also differ from the coals of Rio Grande do Sul analyzed in a previous study.

Santa Catarina

Geochemical and isotopic (Nd-Pb-Sr-O) variations bearing on the genesis of volcanic rocks from Vesuvius, Italy

Alkaline volcanism produced by Monte Somma-Vesuvius volcano includes explosive plinian and subplinian activity in addition to effusive lava flows. Pumice, scoria, and lava (150 samples) exhibit major- and trace-element gradients as a function of SiO2 (58.9-47.2 wt%) and MgO (0-7.8 wt%); Mg value are ???50. Internally gradational chemical groups or cycles are distinguished by age: (1) 25 000 to 14 000 yr B.P.; (2) 8000 yr B.P. to A.D. 79; and (3) A.D. 79 to 1944. A small number of lavas, dikes and scora were also analysed from the Somma formation (~ 35 000 to 25 000 yr B.P.). Within each group, contents of Na2O + K2O increas with decreasing MgO along distinct rocks. Nb/Y values are variable from 0.66 to 3.14 (at SiO2 ??? 50 wt%) generally in the range of alkaline and ultra-alkaline rocks. Variations in contents of some majro elements (e.g., P and Ti), and trace elements (e.g., Th, Nb, Ta, Zr, Hf, Pb, La, and Sc), as well as contrasting trends in ratios of various elements (e.g., Ta/Yb, Hf/U, Th/Ta, Th/Hf, Th/Yb, etc.) are also generally consistent with the group subdivisions. For example, Th/Hf increases from ??? 5 to ??? 10 with decreasing age for the Vesuvius system as a whole, yielding similar compositions in the least evolved rocks (low-silica, high-MgO, imcompatible element-poor) erupted at the end of each cycle. Internal variations within individual eruptions also systematically changed generally towards a common mafic composition at the end of each cycle, thus reflecting the dominanit volume in the magma chamber. At the start of a new eruptive cycle, the rocks are relatively enriched in incompatible elements; younger groups also contain higher abundances than other groups. N-MORB-normalized multielement diagrams exhibit selective enrichments of Sr, K, Rb, Th, and the light rare-earth elements; deep Nb and Ta negative anomalies commonly seen in rocks generated at orogenic margins are absent in the light rare-earth elements; deep Nb and Ta netgative anomalies commonly seen in rocks generated at orogenic margins are absent in our samples. Sr isotopic compositions are known to be variable within some of the units, in agreement with our data (87Sr/86Sr ~ 0.70699 to 0.70803) and with contributions from several isotopic components. Isotopic compositions for ??18O (7.3 to 10.2%), Pb for mineral separates and whole rocks (206Pb/204Pb ~ 18.947 to 19.178, 207Pb/204/Pb ~ 15.617 to 15.769, 208Pb/204Pb ~38.915 to 39.345), and Nd (143Nd ~ 0.51228 to 0.51251) also show variability. Oxygen isotope data show that pumices have higher ??18O values than cogenetic lavas, and that ??18O values and SiO2 are correlated. Radiogenic and stable isotope data plot within range of isotopic compositions for the Roman comagmatic province. Fractional crystallization cannot account for the radiogenic isotopic compositions of the Vesuvius magmas. We favor instead the combined effects of heterogeneous magma sources, together with isotopic exchange near the roof of the magma chamber. We suggest that metasomatized continental mantle lithosphere is the principal source of the magmas. This kind of enriched mantle was melted and reactivated in an area of continental extension (incipient rift setting) without direct reliance on contemporaneous subduction processes but possibly with input from mantle sources that resemble those that produce ocean island basalts.

Journal of Volcanology and Geothermal Research

Melt generation sources and conditions in the wake of a migrating slab window: Geochemistry and petrology of the million-year history of primitive volcanism at Clear Lake volcanic field, California

Clear Lake volcanic field (CLVF) is the northernmost and youngest (~2.2 Ma to 8 ka) of the volcanic centers distributed along the San Andreas transform fault in western California. The initial phase of CLVF volcanism (interval one) occurred between ~2.2 and 1.3 Ma and extends ~35 km southeast of Clear Lake, forming a semi-continuous upland plateau capped by lava flows, with isolated volcanic remnants on the periphery. This volcanism is broadly characterized by geochemically primitive compositions that reflect three source compositions and conditions of melt generation. (1) Partial melting of upwelling asthenospheric mantle lherzolite at moderate pressures (1.2–1.4 GPa) and temperatures (1297–1329 °C) produced high-CaO (9.8–11.3 wt %) basalts with high Al 2 O 3 (16.8–17.6 wt %), Mg#s (66–70), MgO (8–10 wt %), Ni (103–262 μg/g), and Cr (284–609 μg/g). These high-CaO basalts contain olivine (Fo 87–91 ) phenocrysts with Cr-spinel inclusions ± subordinate plagioclase and crop out only in the southern part of the CLVF. (2) Partial melting of depleted sub-continental lithospheric mantle harzburgite at variable pressures (0.7–1.5 GPa) and temperatures (1097–1299 °C) produced a compositional continuum of med-K 2 O, calc-alkaline, high-MgO basalts through high-MgO andesites with high Mg#s (67–77), MgO (8–14 wt %) and high Ni and Cr abundances (154–439 and 340–1124 μg/g, respectively). Mineral assemblages are olivine (Fo 88–93 ) with Cr-spinel inclusions ± subordinate clinopyroxene, orthopyroxene and plagioclase. Small (<2.5 cm) mantle harzburgite xenoliths and mantle olivine xenocrysts are also found in several of these samples. These high-MgO basalts through andesites represent the largest volume of primitive compositions and have erupted predominantly along the main, fault-controlled northwest-southeast trending axis of volcanism with peripheral outcrops to the north, west, and east. (3) Partial melting of the Gorda eclogite slab edge produced adakitic silicic slab melts with strong depletion in the heavy rare earth elements (Yb = 0.6 μg/g). Subsequent reaction of those melts with depleted ultramafic rocks during ascent imprinted the adakitic dacites with high Mg#s (65–78) and elevated Ni (117–210 μg/g) and Cr (191–283 μg/g). Phenocrysts of orthopyroxene (En 87–94 ) with spinel inclusions (Cr# = 80–88) and extremely Ni-rich (9483 μg/g) olivine cores (Fo 84–93 ) record those reactions. Small-volume outcrops of the adakites on the eastern periphery of the CLVF track the passing slab edge. The trio of melting sources recorded by early CLVF magmatism reflect the tectonically complex environment and the hot (1097–1329 °C), shallow (0.7–1.5 GPa) melting conditions for these primitive compositions and provide estimates of the heat delivered to the crust. Over time, this flux led to maturation of the CLVF magmatic system toward the more voluminous and silicic volcanism that characterizes the balance of its subsequent volcanic history and maintains the present-day anomalously high heat flow in the region. The current interval (interval four) of volcanic activity at CLVF is characterized by low-volume, fault-controlled eruptions of basaltic andesite and andesite suggestive of mantle magma and heat delivery to the crust, similar to interval one. This analogous activity provides motivation for the current study and begs the question of whether the system is undergoing thermal priming for renewed silicic volcanism.

California

Long-term geochemical surveillance of fumaroles at Showa-Shinzan dome, Usu volcano, Japan

This study investigates 31 years of fumarole gas and condensate (trace elements) data from Showa-Shinzan, a dacitic dome-cryptodome complex that formed during the 1943-1945 eruption of Usu volcano. Forty-two gas samples were collected from the highest-temperature fumarole, named A-1, from 1954 (800??C) to 1985 (336??C), and from lower-temperature vents. Condensates were collected contemporaneously with the gas samples, and we reanalyzed ten of these samples, mostly from the A-1 vent, for 32 cations and three anions. Modeling using the thermochemical equilibrium program, SOLVGAS, shows that the gas samples are mild disequilibrium mixtures because they: (a) contain unequilibrated sedimentary CH4 and NH3; (b) have unequilibrated meteoric water; or (c) lost CO, either by air oxidation or by absorption by the sodium hydroxide sampling solution. SOLVGAS also enabled us to restore the samples by removing these disequilibrium effects, and to estimate their equilibrium oxygen fugacities and amounts of S2 and CH4. The restored compositions contain > 98% H2O with minor to trace amounts of CO2, H2, HCl, SO2, HF, H2S, CO, S2 and CH4. We used the restored gas and condensate data to test the hypotheses that these time-series compositional data from the dome's fumaroles provide: (1) sufficient major-gas data to analyze long-term degassing trends of the dome's magma-hydrothermal system without the influence of sampling or contamination effects; (2) independent oxygen fugacity-versus-temperature estimates of the Showa-Shinzan dacite; (3) the order of release of trace elements, especially metals, from magma; and (4) useful information for assessing volcanic hazards. The 1954-1985 restored A-1 gas compositions confirm the first hypothesis because they are sufficient to reveal three long-term degassing trends: (1) they became increasingly H2O-rich with time due to the progressive influx of meteoric water into the dome; (2) their C/S and S/Cl ratios decreased dramatically while their Cl/F ratios stayed roughly constant, indicating the progressive outgassing of less soluble components (F ??? Cl > S > C) from the magma reservoir; and (3) their H2O/H2, CO2/CO and H2S/SO2 ratios increased significantly in concert with equilibrium changes expected for the ??? 500??C temperature drop. When plotted against reciprocal temperature, the restored-gas log oxygen fugacities follow a tight linear trend from < NNO + 0.5 at > 800??C to NNO + 2.5 at ??? 400??C. This trend largely disproves the second hypothesis because the oxygen fugacities for the < 800??C restored gases can only be explained by mixing of hot magmatic gases with ??? 350??C steam from superheated meteoric water. But above 800??C this trend intersects the opposing linear trend for other Usu eruptive products, implying a log oxygen fugacity of -11.45 at 902??C for the Showa-Shinzan magma. The time-series trace-element data also disprove the third hypothesis because rock- and incrustation-particle contaminants in the condensates account for most of the trace-element variation. Nonetheless, highly volatile elements like B and As are relatively unaffected by this particle contamination, and they show similar time-series trends as Cl and F. Finally, except for infrequent sampling around the 1977 Usu eruption, the results generally confirm the fourth hypothesis, since the time-series trends for the major gases and selected trace elements indicate that, with time, the system cooled, degassed and was infiltrated by meteoric water, all of which are positive signs that volcanic activity declined over the 31-year history. This study also suggests that second boiling of shallow magma within and possibly beneath the cryptodome sustained magmatic degassing for at least 20 years after emplacement.

Journal of Volcanology and Geothermal Research