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Iron oxide minerals in dust-source sediments from the Bodélé Depression, Chad: Implications for radiative properties and Fe bioavailability of dust plumes from the Sahara

Atmospheric mineral dust can influence climate and biogeochemical cycles. An important component of mineral dust is ferric oxide minerals (hematite and goethite) which have been shown to influence strongly the optical properties of dust plumes and thus affect the radiative forcing of global dust. Here we report on the iron mineralogy of dust-source samples from the Bodélé Depression (Chad, north-central Africa), which is estimated to be Earth’s most prolific dust producer and may be a key contributor to the global radiative budget of the atmosphere as well as to long-range nutrient transport to the Amazon Basin. By using a combination of magnetic property measurements, Mössbauer spectroscopy, reflectance spectroscopy, chemical analysis, and scanning electron microscopy, we document the abundance and relative amounts of goethite, hematite, and magnetite in dust-source samples from the Bodélé Depression. The partition between hematite and goethite is important to know to improve models for the radiative effects of ferric oxide minerals in mineral dust aerosols. The combination of methods shows (1) the dominance of goethite over hematite in the source sediments, (2) the abundance and occurrences of their nanosize components, and (3) the ubiquity of magnetite, albeit in small amounts. Dominant goethite and subordinate hematite together compose about 2% of yellow-reddish dust-source sediments from the Bodélé Depression and contribute strongly to diminution of reflectance in bulk samples. These observations imply that dust plumes from the Bodélé Depression that are derived from goethite-dominated sediments strongly absorb solar radiation. The presence of ubiquitous magnetite (0.002–0.57 wt%) is also noteworthy for its potentially higher solubility relative to ferric oxide and for its small sizes, including PM < 0.1 μm. For all examined samples, the average iron apportionment is estimated at about 33% in ferric oxide minerals, 1.4% in magnetite, and 65% in ferric silicates. Structural iron in clay minerals may account for much of the iron in the ferric silicates. We estimate that the mean ferric oxides flux exported from the Bodélé Depression is 0.9 Tg/yr with greater than 50% exported as ferric oxide nanoparticles (<0.1 μm). The high surface-to-volume ratios of ferric oxide nanoparticles once entrained into dust plumes may facilitate increased atmospheric chemical and physical processing and affect iron solubility and bioavailability to marine and terrestrial ecosystems.

Aeolian Research

A regional-scale study of chromium and nickel in soils of northern California, USA

A soil geochemical survey was conducted in a 27,000-km 2 study area of northern California that includes the Sierra Nevada Mountains, the Sacramento Valley, and the northern Coast Range. The results show that soil geochemistry in the Sacramento Valley is controlled primarily by the transport and weathering of parent material from the Coast Range to the west and the Sierra Nevada to the east. Chemically and mineralogically distinctive ultramafic (UM) rocks (e.g. serpentinite) outcrop extensively in the Coast Range and Sierra Nevada. These rocks and the soils derived from them have elevated concentrations of Cr and Ni. Surface soil samples derived from UM rocks of the Sierra Nevada and Coast Range contain 1700-10,000 mg/kg Cr and 1300-3900 mg/kg Ni. Valley soils west of the Sacramento River contain 80-1420 mg/kg Cr and 65-224 mg/kg Ni, reflecting significant contributions from UM sources in the Coast Range. Valley soils on the east side contain 30-370 mg/kg Cr and 16-110 mg/kg Ni. Lower Cr and Ni concentrations on the east side of the valley are the result of greater dilution by granitic sources of the Sierra Nevada. Chromium occurs naturally in the Cr(III) and Cr(VI) oxidation states. Trivalent Cr is a non-toxic micronutrient, but Cr(VI) is a highly soluble toxin and carcinogen. X-ray diffraction and scanning electron microscopy of soils with an UM parent show Cr primarily occurs within chromite and other mixed-composition spinels (Al, Mg, Fe, Cr). Chromite contains Cr(III) and is highly refractory with respect to weathering. Comparison of a 4-acid digestion (HNO 3 , HCl, HF, HClO 4 ), which only partially dissolves chromite, and total digestion by lithium metaborate (LiBO 3 ) fusion, indicates a lower proportion of chromite-bound Cr in valley soils relative to UM source soils. Groundwater on the west side of the Sacramento Valley has particularly high concentrations of dissolved Cr ranging up to 50 ??g L -1 and averaging 16.4 ??g L -1 . This suggests redistribution of Cr during weathering and oxidation of Cr(III)-bearing minerals. It is concluded that regional-scale transport and weathering of ultramafic-derived constituents have resulted in enrichment of Cr and Ni in the Sacramento Valley and a partial change in the residence of Cr.

Applied Geochemistry

Persistent U(IV) and U(VI) following in-situ recovery (ISR) mining of a sandstone uranium deposit, Wyoming, USA

Drill-core samples from a sandstone-hosted uranium (U) deposit in Wyoming were characterized to determine the abundance and distribution of uranium following in-situ recovery (ISR) mining with oxygen- and carbon dioxide-enriched water. Concentrations of uranium, collected from ten depth intervals, ranged from 5 to 1920 ppm. A composite sample contained 750 ppm uranium with an average oxidation state of 54% U(VI) and 46% U(IV). Scanning electron microscopy (SEM) indicated rare high uranium (&sim;1000 ppm U) in spatial association with P/Ca and Si/O attributed to relict uranium minerals, possibly coffinite, uraninite, and autunite, trapped within low permeability layers bypassed during ISR mining. Fission track analysis revealed lower but still elevated concentrations of U in the clay/silica matrix and organic matter (several 10 s ppm) and yet higher concentrations associated with Fe-rich/S-poor sites, likely iron oxides, on altered chlorite or euhedral pyrite surfaces (but not on framboidal pyrite). Organic C (<1.62%), total S (<0.31%), and P (<0.03%) were in low abundance relative to the overall bulk composition. Microbial community analysis showed a diverse group of bacteria present with a wide range of putative metabolisms, and provides evidence for a variety of redox microenvironments co-existing in core samples. Although the uranium minerals persisting in low permeability areas in association with organic carbon were less affected by oxidizing solutions during mining, the likely sequestration of uranium within labile iron oxides following mining and sensitivity to changes in redox conditions requires careful attention during groundwater restoration.

Wyoming

Assessing changes in the physico-chemical properties and fluoride adsorption capacity of activated alumina under varied conditions

Adsorption using activated alumina is a simple method for removing fluoride from drinking water, but to be cost effective the adsorption capacity must be high and effective long-term. The intent of this study was to assess changes in its adsorption capacity under varied conditions. This was determined by evaluating the physico-chemical properties, surface charge, and fluoride (F − ) adsorption capacity and rate of activated alumina under conditions such as hydration period, particle size, and slow vs. fast titrations. X-ray diffraction and scanning electron microscopy analyses show that the mineralogy of activated alumina transformed to boehmite, then bayerite with hydration period and a corresponding reduction in adsorption capacity was expected; while surface area analyses show no notable changes with hydration period or particle size. The pH dependent surface charge was three times higher using slow potentiometric titrations as compared to fast titrations (due largely to diffusion into pore space), with the surface acidity generally unaffected by hydration period. Results from batch adsorption experiments similarly show no change in fluoride adsorption capacity with hydration period. There was also no notable difference in fluoride adsorption capacity between the particle size ranges of 0.5–1.0 mm and 0.125–0.250 mm, or with hydration period. However, adsorption rate increased dramatically with the finer particle sizes: at an initial F − concentration of 0.53 mmol L −1 (10 mg L −1 ), 90% was adsorbed in the 0.125–0.250 mm range after 1 h, while the 0.5–1.0 mm range required 24 h to achieve 90% adsorption. Also, the pseudo-second-order adsorption rate constants for the finer vs. larger particle sizes were 3.7 and 0.5 g per mmol F − per min respectively (24 h); and the initial intraparticle diffusion rate of the former was 2.6 times faster than the latter. The results show that adsorption capacity of activated alumina remains consistent and high under the conditions evaluated in this study, but in order to increase adsorption rate, a relatively fine particle size is recommended.

Applied Geochemistry

Natural attenuation can lead to environmental resilience in mine environment

Four streams flowing in the Iglesiente and Arburese mine districts (SW Sardinia, Italy), exploited for zinc (Zn) and lead (Pb) extraction from sulphides and secondary non-sulphide mineralization (calamine ores), have been studied combining investigations from the macroscale (hydrologic tracer techniques) to the microscale (X-ray powder diffraction, scanning electron microscopy, X-ray absorption spectroscopy). In the investigated area, concerns arise from release of metals to water during weathering of ore minerals and mine-waste. Specifically, Zn is observed at extremely high concentrations (10s of mg/L or more) in waters in some of the investigated catchments. The results from synoptic sampling campaigns showed marked differences of Zn loads, from 6.3 kg/day (Rio San Giorgio) to 2000 kg/day (Rio Irvi). Moreover, natural attenuation of metals was found to occur i) through precipitation of Fe compounds (Fe oxy/hydroxides and “green rust”), ii) by means of the authigenic formation of metal sulphides promoted by microbial sulphate reduction, iii) by metal intake in roots and stems of plants ( Phragmites australis and Juncus acutus ) and by immobilization in the rhizosphere, and iv) by cyanobacterial biomineralization processes that lead to formation of Zn-rich phases (hydrozincite and amorphous Zn-silicate) The biologically mediated natural processes that lead to significant abatement and/or reduction of metal loads, are the response of environmental systems to perturbations caused from mine activities, and can be considered part of the resilience of the system itself. The aim of this study is to understand the effect of these processes on the evolution of the studied systems towards more stable and, likely, resilient conditions, e.g. by limiting metal mobility and favoring the improvement of the overall quality of water. The understanding of how ecosystems adapt and respond to contamination, and which chemical and physical factors control these natural biogeochemical barriers, can help to plan effective remediation actions.

Sardinia

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

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

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 Paran&aacute; 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 Le&atilde;o-Buti&aacute; 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 Paran&aacute; 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, Paran&aacute; 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 Le&atilde;o-Buti&aacute; 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

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

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

Scanning electron microscopic evaluation of broad ion beam milling effects to sedimentary organic matter: Sputter-induced artifacts or naturally occurring porosity?

Research examining organic-matter hosted porosity has significantly increased during the last decade due to greater focus on understanding hydrocarbon migration and storage in source-rock reservoirs, and technological advances in scanning electron microscopy (SEM) capabilities. The examination of nanometer-scale organic-matter hosted porosity by SEM requires the preparation of exceptionally flat geologic samples beyond the abilities of traditional mechanical polishing, which can deform or otherwise obscure organic surfaces. To meet this demand, broad ion beam (BIB) milling was introduced as a sample preparation technique for SEM petrographic analysis of geologic samples. As with any sample preparation technique, there can be unintended consequences. In this study, we examined the development of nanometer-scale sputter-induced voids caused by BIB milling of thermoset plastic binder material [poly(methyl methacrylate), PMMA] used for the mounting of geologic samples, and artifact sputter-induced voids in the organic matter of Green River Formation and Kimmeridge Clay Formation source rocks. Development of artifact sputter-induced voids was evaluated in relation to variations in the slope of the sample examination surface (0.0–4.9% slope), effectively varying the angle of ion incidence. The results indicate that only minor variations in the angle of ion incidence can generate sputter-induced voids in both PMMA (10.0–386.2 nm diameter sputter-induced voids) and sample sedimentary organic matter (solid bitumen; 12.2–103.6 nm diameter sputter-induced voids). Overall, average artifact pore diameters increased with increasing ion incidence angle within PMMA. Although sputter-induced voids within solid bitumen in the Green River Formation sample were only found in limited extent, the size of these void artifacts falls within the same size range as naturally occurring meso-macroporosity. That is, the pore-like artifacts could easily be misconstrued as naturally developed organic porosity, which is a major concern for SEM-based porosity evaluation methods. This study describes the factors that contribute to the creation of artifact sputter-induced voids, their distinguishing characteristics, and best practices for avoiding the creation of ion-induced artifacts.

International Journal of Coal Geology

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

Optical and biochemical properties of a southwest Florida whiting event

“Whiting” in oceanography is a term used to describe a sharply defined patch of water that contains high levels of suspended, fine-grained calcium carbonate (CaCO 3 ). Whitings have been reported in many oceanic and lake environments, and recently have been reported in southwest Florida coastal waters. Here, field and laboratory measurements were used to study optical, biological, and chemical properties of whiting waters off southwest Florida. No significant difference was found in chlorophyll a concentrations between whiting and outside waters (non-whiting water), but average particle backscattering coefficients in whiting waters were double those in outside waters, and remote sensing reflectance in whiting waters was higher at all wavelengths (400–700 nm). While other potential causes cannot be completely ruled out, particle composition and biochemical differences between sampled whiting water, contiguous water, and outside water indicate a biologically precipitated mode of whiting formation. Taxonomic examination of marine phytoplankton samples collected during a whiting event revealed a community dominated by autotrophic picoplankton and a small (<10 μm), centric diatom species, identified as Thalassiosira sp. through the use of scanning electron microscopy. Amorphous to fully formed crystals of CaCO 3 were observed along the girdle bands of Thalassiosira sp. cells and autotrophic picoplankton cells. Although carbonate parameters differed from whiting and contiguous to outside water, more sampling is needed to determine if these results are statistically significant.

Florida

Biogeochemical transformation of Fe minerals in a petroleum-contaminated aquifer

The Bemidji aquifer in Minnesota, USA is a well-studied site of subsurface petroleum contamination. The site contains an anoxic groundwater plume where soluble petroleum constituents serve as an energy source for a region of methanogenesis near the source and bacterial Fe(III) reduction further down gradient. Methanogenesis apparently begins when bioavailable Fe(III) is exhausted within the sediment. Past studies indicate that Geobacter species and Geothrix fermentens -like organisms are the primary dissimilatory Fe-reducing bacteria at this site. The Fe mineralogy of the pristine aquifer sediments and samples from the methanogenic (source) and Fe(III) reducing zones were characterized in this study to identify microbiologic changes to Fe valence and mineral distribution, and to identify whether new biogenic mineral phases had formed. Methods applied included X-ray diffraction; X-ray fluorescence (XRF); and chemical extraction; optical, transmission, and scanning electron microscopy; and Mössbauer spectroscopy. All of the sediments were low in total Fe content (≈ 1%) and exhibited complex Fe-mineralogy. The bulk pristine sediment and its sand, silt, and clay-sized fractions were studied in detail. The pristine sediments contained Fe(II) and Fe(III) mineral phases. Ferrous iron represented approximately 50% of Fe TOT . The relative Fe(II) concentration increased in the sand fraction, and its primary mineralogic residence was clinochlore with minor concentrations found as a ferroan calcite grain cement in carbonate lithic fragments. Fe(III) existed in silicates (epidote, clinochlore, muscovite) and Fe(III) oxides of detrital and authigenic origin. The detrital Fe(III) oxides included hematite and goethite in the form of mm-sized nodular concretions and smaller-sized dispersed crystallites, and euhedral magnetite grains. Authigenic Fe(III) oxides increased in concentration with decreasing particle size through the silt and clay fraction. Chemical extraction and Mössbauer analysis indicated that this was a ferrihydrite like-phase. Quantitative mineralogic and Fe(II/III) ratio comparisons between the pristine and contaminated sediments were not possible because of textural differences. However, comparisons between the texturally-similar source (where bioavailable Fe(III) had been exhausted) and Fe(III) reducing zone sediments (where bioavailable Fe(III) remained) indicated that dispersed detrital, crystalline Fe(III) oxides and a portion of the authigenic, poorly crystalline Fe(III) oxide fraction had been depleted from the source zone sediment by microbiologic activity. Little or no effect of microbiologic activity was observed on silicate Fe(III). The presence of residual “ferrihydrite” in the most bioreduced, anoxic plume sediment (source) implied that a portion of the authigenic Fe(III) oxides were biologically inaccessible in weathered, lithic fragment interiors. Little evidence was found for the modern biogenesis of authigenic ferrous-containing mineral phases, perhaps with the exception of thin siderite or ferroan calcite surface precipitates on carbonate lithic fragments within source zone sediments.

Geochimica et Cosmochimica Acta

Ancient wet aeolian environments on Earth: Clues to presence of fossil/live microorganisms on Mars

Ancient wet aeolian (wet-sabkha) environments on Earth, represented in the Entrada and Navajo sandstones of Utah, contain pipe structures considered to be the product of gas/water release under pressure. The sediments originally had considerable porosity allowing the ingress of living plant structures, microorganisms, clay minerals, and fine-grained primary minerals of silt and sand size from the surface downward in the sedimentary column. Host rock material is of a similar size and porosity and presumably the downward migration of fine-grained material would have been possible prior to lithogenesis and final cementation. Recent field emission scanning electron microscopy (FESEM) and EDS (energy-dispersive spectrometry) examination of sands from fluidized pipes in the Early Jurassic Navajo Sandstone reveal the presence of fossil forms resembling fungal filaments, some bearing hyphopodium-like structures similar to those produced by modern tropical leaf parasites. The tropical origin of the fungi is consistent with the paleogeography of the sandstone, which was deposited in a tropical arid environment. These fossil fungi are silicized, with minor amounts of CaCO3 and Fe, and in some cases a Si/Al ratio similar to smectite. They exist as pseudomorphs, totally depleted in nitrogen, adhering to the surfaces of fine-grained sands, principally quartz and orthoclase. Similar wet aeolian paleoenvironments are suspected for Mars, especially following catastrophic sediment-charged floods of enormous magnitudes that are believed to have contributed to rapid formation of large water bodies in the northern plains, ranging from lakes to oceans. These events are suspected to have contributed to a high frequency of constructional landforms (also known as pseudocraters) related to trapped volatiles and water-enriched sediment underneath a thick blanket of materials that were subsequently released to the martian surface, forming piping structures at the near surface and constructional landforms at the surface. This constructional process on Mars may help unravel the complex history of some of the piping structures observed on Earth; on Earth, evidence for the constructional landforms has been all but erased and the near-surface piping structures exposed through millions of years of differential erosion and topographic inversion now occur as high-standing promontories. If the features on both Earth and Mars formed by similar processes, especially involving water and other volatiles, and since the piping structures of Earth provided suitable environments for life to thrive in, the martian features in the northern plains should be considered as prime targets for physico/mineral/chemical/microbiological analyses once the astrobiological exploration of the red planet begins in earnest. ?? 2004 Elsevier Inc. All rights reserved.

Icarus

Weakening of ice by magnesium perchlorate hydrate

We show that perchlorate hydrates, which have been detected at high circumpolar martian latitudes, have a dramatic effect upon the rheological behavior of polycrystalline water ice under conditions applicable to the North Polar Layered Deposits (NPLD). We conducted subsolidus creep tests on mixtures of ice and magnesium perchlorate hydrate, Mg(ClO4)2·6H2O (MP6), of 0.02, 0.05, 0.10, and 0.47 volume fraction MP6. We found these mixtures to be increasingly weak with increasing MP6 content. For mixtures with ⩽0.10 volume fraction MP6, we resolved a stress exponent of n ≈ 2 at low stresses transitioning to n ≈ 4 above 10 MPa. Scanning electron microscopy of deformed specimens revealed MP6 to be distributed as an interconnected film between ice grains. These results suggest that grain boundary sliding (GBS) may be enhanced with respect to pure ice. As the enhancement of GBS is expected in polycrystalline aggregates containing a few percent melt or otherwise weak material distributed along grain boundaries, the observed n ≈ 2 is consistent with the mutual accommodation of basal slip and GBS. If ice containing trace concentrations of MP6 is also much weaker than pure ice at low stresses, flow in the NPLD could be significantly enhanced, particularly at the warmer basal temperatures associated with higher martian obliquities.

Icarus

Reaction kinetics and accelerant effects of sulfides in early mature hydrocarbon generation using hydrous pyrolysis

Hydrocarbon generation in organic-rich sediments is influenced by the molecular organic composition and relative abundance of associated minerals. Certain mineral-derived elements act as catalysts and reaction intermediaries, facilitating early-stage hydrocarbon formation in potential source rocks. This study investigated the role of sulfur contributed from pyrite as an accelerant in thermal reaction, focusing on its effects on early maturation and consequent hydrocarbon generation from gilsonite (low-sulfur solid petroleum). Hydrous pyrolysis (HP) experiments were conducted on mixtures of gilsonite and pyrite in varying ratios (1:0.1, 1:0.5, 1:1, 1:2, and 1:10 w/w gilsonite:pyrite) at 320, 350, and 370 °C for 72 h. Untreated and thermally altered residues were analyzed using solid bitumen reflectance (BR o , %), total organic carbon (TOC) content, programmed temperature pyrolysis, scanning electron microscopy with energy-dispersive spectroscopy (SEM-EDS), and X-ray diffraction (XRD) to evaluate the potential accelerant role of pyritic sulfur in hydrocarbon formation. The results show HP residues at 320 and 350 °C with greater pyrite concentrations had higher BR o , while reflectance values were similar in the 370 °C residues, regardless of pyrite concentration, suggesting enhanced reaction at lower thermal conditions. Increasing pyrite content systematically decreased hydrogen index (HI) values while increasing the transformation ratio (TR) and production index (PI), indicating enhanced conversion of organic matter to hydrocarbons with increasing pyrite concentrations. Gas yields increased with pyrite addition, particularly at 350 °C, confirming secondary cracking effects. However, gas production stabilized or declined at higher pyrite loadings (1:10), suggesting alternative reaction pathways such as coke formation. Our data indicate the presence of pyrite lowers the activation energy for thermal cracking, shifting peak experimental hydrocarbon generation temperatures downward by 20–30 °C, with the most pronounced accelerant effects observed at moderate pyrite concentrations (1:0.5 and 1:1). The thermodynamic framework reveals that pyrite stability is influenced by experimental conditions, with pyrrhotite formation favored in the presence of gilsonite due to reduced oxygen fugacity. Pyrite transformation to pyrrhotite, as observed through XRD, SEM-EDS, and predicted by thermodynamic data, further supports the accelerant role of S, as pyrrhotite exhibits a higher hydrogen transfer potential, promoting early oil generation. These findings highlight the importance of pyrite in modulating hydrocarbon generation pathways in organic-rich systems.

Journal of Analytical and Applied Pyrolysis

Complex resistivity signatures of ethanol biodegradation in porous media

Numerous adverse effects are associated with the accidental release of ethanol (EtOH) and its persistence in the subsurface. Geophysical techniques may permit non-invasive, real time monitoring of microbial degradation of hydrocarbon. We performed complex resistivity (CR) measurements in conjunction with geochemical data analysis on three microbial-stimulated and two control columns to investigate changes in electrical properties during EtOH biodegradation processes in porous media. A Debye Decomposition approach was applied to determine the chargeability ( m ), normalized chargeability ( m n ) and time constant ( &tau; ) of the polarization magnitude and relaxation length scale as a function of time. The CR responses showed a clear distinction between the bioaugmented and control columns in terms of real ( &sigma;&prime; ) and imaginary ( &sigma;&Prime; ) conductivity, phase ( ϕ ) and apparent formation factor ( F app ). Unlike the control columns, a substantial decrease in &sigma;&prime; and increase in F app occurred at an early time (within 4 days) of the experiment for all three bioaugmented columns. The observed decrease in &sigma;&prime; is opposite to previous studies on hydrocarbon biodegradation. These columns also exhibited increases in ϕ (up to ~ 9 mrad) and &sigma;&Prime; (up to two order of magnitude higher) 5 weeks after microbial inoculation. Variations in m and m n were consistent with temporal changes in ϕ and &sigma;&Prime; responses, respectively. Temporal geochemical changes and high resolution scanning electron microscopy imaging corroborated the CR findings, thus indicating the sensitivity of CR measurements to EtOH biodegradation processes. Our results offer insight into the potential application of CR measurements for long-term monitoring of biogeochemical and mineralogical changes during intrinsic and induced EtOH biodegradation in the subsurface.

Journal of Contaminant Hydrology