Electron probe microanalysis of minerals: Microanalyzer or scanning electron microscope?

The results of electron probe microanalysis of several rock-forming minerals by wavelength-dispersive spectrometry (WDS) and energy-dispersive spectrometry (EDS) are compared, and the metrological characteristics of both methods are studied. The measurements were made with the use of a JXA-8100 (JEOL) microanalyzer with five wavelength-dispersive spectrometers and a MIRA 3 LMU (Tescan) scanning electron microscope equipped with an INCA Energy 450 XMax 80 (Oxford Instruments) microanalysis system. Specimens with olivine, garnet, pyroxene, ilmenite, and Cr-spinel grains were analyzed.The variation coefficients that characterize the repeatability of a single determination are found to be ~ 0.5% for WDS and ~ 0.9% for EDS in the compositional range of the main components (C > 10%). For minor components (1% < C < 10%), the variation coefficients are 1.4% and 3.0%, respectively, and for impurities (0.3% < C < 1%), 2.7% and 13%, respectively. For lower contents EDS is almost inapplicable. The ratio of the results obtained by the two methods is reproduced with high precision: For major components, the variation coefficient is 0.56%; for minor components, 1.7%; and even for impurities, it is ~ 8%. The magnitude of the bias is between 0.2 and 3.2 rel.%, which is acceptable.The results show that the accuracies of WDS and EDS are similar for measuring major and minor components of rock-forming minerals. Energy-dispersive spectrometry is inferior to wavelength-dispersive spectrometry for impurities and is completely inapplicable for still lower contents. This method is easier to implement, and the results are available soon after switching on the instrument. Wavelength-dispersive spectrometry needs more time for preparation, but it ensures a precise high-efficiency large-scale analysis of samples of similar compositions, even when the element contents are lower than 1%.     

The scale effect on the soil spatial heterogeneity of Haloxylon ammodendron (C. A. Mey.) in a sandy desert

Haloxylon ammodendron Bge (C.A. Mey.) is a dominant shrub species in the Gurbantonggut Desert and plays an important role in preventing wind erosion and combating desertification, typically by developing fertile islands in desert ecosystems; however, such islands often depend on the scales. An experiment was conducted to determine the scale dependence for the soil spatial heterogeneity of H. ammodendron in the Gurbantonggut Desert using the soil pH, electrical conductivity (EC), soil organic carbon (SOC), and total nitrogen (TN). The results showed that the soil EC, SOC and TN were significantly higher at the individual scale than the population scale. Moreover, the coefficients of variation (CV %) of the soil parameters at the individual scale were greater than they were at the population scale, with all except for pH (CV = 4.35 % for individual scale and CV = 2.87 % for population scale) presenting a moderate degree of variability (10 % < CV < 100 %). A geostatistical analysis revealed a strong spatial dependence [C ₀ /(C ₀ + C) < 25 %] within the distance of ranges for the tested parameters at both scales. The kriging interpolation results presented significant accumulation of soil SOC and TN around the shrub center and formed a significant “fertile island” at the individual scale, whereas the soil EC was much lower at the shrub center. At the population scale, patch fragments of the soil chemical properties were observed; however, not all individuals presented significant fertile islands or salt islands, and the soil EC presented a similar distribution as SOC and TN. These differences suggested that different mechanisms controlled the spatial distribution of soil minerals at the two scales and that the spatial heterogeneities are scale-dependent in a desert ecosystem.     

Comparison of Cu,Zn and Fe bioleaching from Cu-metallurgical slags in the presence of Pseudomonas fluorescens and Acidithiobacillus thiooxidans

Metal leaching from metallurgical wastes (slags) by means of environmentally friendly approaches is promising for practical applications. The goal of this study was to compare the feasibility of metal bioleaching from Cu slags by means of Pseudomonas fluorescens and Acidithiobacillus thiooxidans. Two size particles (<0.3 mm and 1–2 mm) of two types of Cu slags (massive crystalline slag and granulated amorphous slag) were used to study metal (Cu, Zn and Fe) bioleaching. The 40-days bioleaching experiments with P. fluorescens began at circumneutral pH (7.0), whereas the experiments with A. thiooxidans were started under acidic (pH 2.5) conditions. The results demonstrated that A. thiooxidans catalyzes metal leaching from both slag types investigated. After 21 days of incubation, optimal leaching was achieved and up to 79% Cu, 76% Zn and 45% Fe could be extracted from crystalline slag under conditions of 1 wt.% pulp density and particle size <0.3 mm. The optimal efficiency achieved with amorphous slag was 81% Cu, 79% Zn and 22% Fe when 1% pulp density and 1–2 mm particle size were used. The use of P. fluorescens resulted in poor leaching efficiencies as compared to the performance of A. thiooxidans, presumably due to the higher pH conditions maintained during the P. fluorescens incubations. The maximum metal leaching efficiencies with P. fluorescens were achieved at 1% pulp density and particle size <0.3 mm and did not exceed 10% Cu, 4% Zn, 0.3% Fe for crystalline slag and 4% Cu, 3% Zn, 0.7% Fe for amorphous slag. Both slags exhibited a good potential for bioleaching with A. thiooxidans, however; further optimization of the process parameters (e.g. pulp density, particle size and pH) is needed to improve the efficiency.     

C-S-Fe relationships and the isotopic composition of pyrite in the New Albany Shale of the Illinois Basin,U.S.A.

The relationship between pyritic sulfur content (S_pyr) and organic carbon content (C_org) of shales analyzed from the New Albany Group depends upon C_org. For samples of <6 wt.% C_org, S_pyt, and C_org are strongly correlated (r = 0.85). For C_org-“rich” shales (>6 wt.%), no S_pty-C_org, correlation is apparent. The degree of Fe pyritization (DOP) shows similar relationships to C_org. These C-S-Fe relationships suggest that pyrite formation was limited by the availability of metabolizable organic carbon in samples where C_org < 6 wt.% and by the availability of reactive Fe for samples where C_org > 6 wt.%. Apparent sulfur isotope fractionations relative to contemporaneous seawater sulfate (Δ³⁴S) for pyrite formation average −40% for non-calcareous shales and −25%. for calcareous shales. Δ³⁴S values become smaller with increasing C_org, S_pyt, and DOP for all C_org-“poar” (<6 wt%) and some C_org-“nch” (<6 wt.%) shales. These trends suggest that pyrite formation occurred in a closed system or that instantaneous bacterial fractionation for sulfate reduction decreased in magnitude with increasing organic carbon content. The isotopic trends observed in the New Albany Group are not necessarily representative of other shales having a comparable range of organic carbon content, e.g. Cretaceous shales and mudstones from the western interior of North America (GAUTIER, 1986). Δ³⁴S values in the remainder of the C_org-rich New Albany Group shales are relatively large (−38 to −47%.) and independent of C_org, S_pyr, and DOP, which suggests that pyrite in these shales formed mostly at or above the sediment-water interface by precipitation from an isotopically uniform reservoir of dissolved H₂S.     

Measurements of hillslope debris flow impact pressure on obstacles

We present measurements of hillslope debris flow impact pressures on small obstacles. Two impact sensors have been installed in a real-scale experimental site where 50?m³ of water-saturated soil material are released from rest. Impact velocities vary between 2 and 13?m/s; flow heights between 0.3 and 1.0?m. The maximum impact pressures measured over 15 events represent between 2 and 50 times the equivalent static pressures. The measurements reveal that quadratic velocity-dependent formulas can be used to estimate impact pressures. Impact coefficients C are constant from front to tail and range between 0.4?<?C?<?0.8 according to the individual events. The pressure fluctuations to depend on the sensor size and are between 20% and 60% of the mean pressure values. Our results suggest that hazard guidelines for hillslope debris flows should be based on quadratic velocity-dependent formulas.     

Gases in Taiwan mud volcanoes: Chemical composition,methane carbon isotopes,and gas fluxes

Mud volcanoes are important pathways for CH₄ emission from deep buried sediments; however, the importance of gas fluxes have hitherto been neglected in atmospheric source budget considerations. In this study, gas fluxes have been monitored to examine the stability of their chemical compositions and fluxes spatially, and stable C isotopic ratios of CH₄ were determined, for several mud volcanoes on land in Taiwan. The major gas components are CH₄ (>90%), “air” (i.e. N₂ + O₂ + Ar, 1–5%) and CO₂ (1–5%) and these associated gas fluxes varied slightly at different mud volcanoes in southwestern Taiwan. The Hsiao-kun-shui (HKS) mud volcano emits the highest CH₄ concentration (CH₄ > 97%). On the other hand, the Chung-lun mud volcano (CL) shows CO₂ up to 85%, and much lower CH₄ content (<37%). High CH₄ content (>90%) with low CO₂ (<0.2%) are detected in the mud volcano gases collected in eastern Taiwan. It is suggestive that these gases are mostly of thermogenic origin based on C₁ (methane)/C₂ (ethane) + C₃ (propane) and δ¹³C_CH4 results, with the exception of mud volcanoes situated along the Gu-ting-keng (GTK) anticline axis showing unique biogenic characteristics. Only small CH₄ concentration variations, <2%, were detected in four on-site short term field-monitoring experiments, at Yue-shi-jie A, B, Kun-shui-ping and Lo-shan A. Preliminary estimation of CH₄ emission fluxes for mud volcanoes on land in Taiwan fall in a range between 980 and 2010 tons annually. If soil diffusion were taken into account, the total amount of mud volcano CH₄ could contribute up to 10% of total natural CH₄ emissions in Taiwan.     

New collectors for sphalerite flotation

A series of N-arylhydroxamic acids (31) were synthesized and tested as collectors to float sphalerite from a Canadian copper–zinc ore. The compounds were classified into four types namely, N-aryl-C-alkyl, N-aryl-C-aryl, N-aryl-C-aralkyl, and dihydroxamic acids based on the type of substitution. Dihydroxamic acids were found to be poor mineral collectors while the efficiency of sphalerite flotation increased in the order N-aryl-C-aryl < N-aryl-C-alkyl < N-aryl-C-aralkyl. Sphalerite was floated without activation by copper sulfate, and the best sphalerite recovery of about 80% (grade 32%) was achieved with N-hydrocinnamoyl-N-phenylhydroxylamine (HCNPHA) 67 g/t collector dosage. However, pyrite also floated along with sphalerite and this appeared as a major disadvantage to be addressed.     

Evaluation of the use of legumes for biodegradation of petroleum hydrocarbons in soil

The aim of this research was to evaluate the potential of six legumes: Medicago sativa L., Glycine max, Arachis hypogea, Lablab purpureus, Pheseolus vulgaris and Cajanus cajan to restore within a short period of time soil contaminated with 3% crude oil. The legumes in five replications were grown in crude oil-contaminated and crude oil-uncontaminated soil in a completely randomized design. Plants were assessed for seedling emergence, plant height and leaf number. GC–MS was used to analyze the residual crude oil from the rhizosphere of the legumes. Plant growth parameters were reduced significantly (P < 0.05) for legumes in contaminated soil compared to their controls. In the 4th week after planting (WAP), shoot height increased across the species up to the 8th WAP. However, in the 12 WAP no significant increase in the shoot of all species was observed. Two WAP legumes planted in contaminated soil had significantly (P < 0.05) higher leaf number than these planted in uncontaminated soil with the exception of M. sativa. In the 4th WAP, only A. hypogea and P. vulgaris had increased leaf number, while in the 6th WAP, only L. purpureus had increased leaf number and survived up to the 12th WAP while most of the legumes species died. Chromatographic profiles indicated 100% degradation of the oil fractions in C. cajan and L. purpureus after 90 days. For other legumes however, greater losses of crude oil fractions C₁–C₁₀ and C₁₀–C₂₀ were indicated in rhizosphere soil of P. vulgaris and G. max, respectively. The most effective removal (93.66%) of C₂₁–C₃₀ components was observed in G. max-planted soil even though vegetation was not established. The legumes especially C. cajan, L. purpureus and A. hypogea are promising candidates for phytoremediation of petroleum hydrocarbon-impacted soil.     

Chemical and carbon isotopic evolution of hydrocarbons during prograde metamorphism from 100°C to 550°C: Case study in the Liassic black shale formation of Central Swiss Alps

Hydrocarbon distributions and stable isotope ratios of carbonates (δ¹³C_car, δ¹⁸O_car), kerogen (δ¹³C_ker), extractable organic matter (δ¹³C_EOM) and individual hydrocarbons of Liassic black shale samples from a prograde metamorphic sequence in the Swiss Alps were used to identify the major organic reactions with increasing metamorphic grade. The studied samples range from the diagenetic zone (<100°C) to amphibolite facies (∼550°C). The samples within the diagenetic zones (<100 and 150°C) are characterized by the dominance of C_<20n-alkanes, suggesting an origin related with marine and/or bacterial inputs. The metamorphic samples (200 to 550°C) have distributions significantly dominated by C₁₂ and C₁₃n-alkanes, C₁₄, C₁₆ and C₁₈n-alkylcyclopentanes and to a lesser extend C₁₅, C₁₇ and C₂₁n-alkylcyclohexanes. The progressive ¹³C-enrichment (up to 3.9‰) with metamorphism of the C_>17n-alkanes suggests the occurrence of cracking reactions of high molecular weight compounds. The isotopically heavier (up to 5.6‰) C_<17n-alkanes in metamorphic samples are likely originated by thermal degradation of long-chain homologous with preferential release of isotopically light C₁ and C₂ radicals. The dominance of specific even C-number n-alkylcyclopentanes suggests an origin related to direct cyclization mechanism (without decarboxylation step) of algal or bacterial fatty acids occurring in reducing aqueous metamorphic fluid conditions. The regular increase of the concentrations of n-alkylcycloalkanes vs. C_>13n-alkanes with metamorphism suggests progressive thermal release of kerogen-linked fatty acid precursors and degradation of n-alkanes. Changes of the steroid and terpenoid distributions are clearly related to increasing metamorphic temperatures. The absence of 18α(H)-22,29,30-trisnorneohopane (Ts), the occurrence of 17β(H)-trisnorhopane, 17β(H), 21α(H)-hopanes in the C₂₉ to C₃₁ range and 5α(H),14α(H),17α(H)-20R C₂₇, C₂₉ steranes in the low diagenetic samples (<100°C) are characteristic of immature bitumens. The higher thermal stress within the upper diagenetic zone (150°C) is marked by the presence of Ts, the disappearance of 17β(H)-trisnorhopane and thermodynamic equilibrium of the 22S/(22S + 22R) homohopane ratios. The increase of the ααα-sterane 20S/(20S + 20R) and 20R ββ/(ββ + αα) ratios (from 0.0 to 0.55 and from 0.0 to 0.40, respectively) in the upper diagenetic zone indicates the occurrence of isomerization reactions already at <150°C. However, the isomerization at C-20 (R → S) reaches thermodynamic equilibrium values already at the upper diagenesis (∼150°C) whereas the epimerisation at C-14 and C-17 (αα → ββ) arrives to constant values in the lower anchizone (∼200°C). The ratios Ts vs. 17α(H)-22,29,30-trisnorneohopane [(Ts/(Ts + Tm)] and 18α(H)-30-norneohopane (C₂₉Ts) vs. 17α(H),21β(H)-30-norhopane [C₂₉Ts/(C₂₉Ts + C₂₉)] increase until the medium anchizone (200 to 250°C) from 0.0 to 0.96 and from 0.0 to 0.44, respectively. An opposite trend towards lower values is observed in the higher metamorphic samples.The occurrence of specific hydrocarbons (e.g., n-alkylcyclopentanes, cadalene, hydrogenated aromatic compounds) in metamorphic samples points to kerogen degradation reactions most probably occurring in the presence of water and under reducing conditions. The changes of hydrocarbon distributions and carbon isotopic compositions of n-alkanes related to metamorphism suggest that the organic geochemistry may help to evaluate the lowest grades of prograde metamorphism.     

Early diagenetic remineralization of sedimentary organic C in the Gulf of Papua deltaic complex (Papua New Guinea): Net loss of terrestrial C and diagenetic fractionation of C isotopes

Oceania supplies ∼40% of the global riverine flux of organic carbon, approximately half of which is injected onto broad continental shelves and processed in shallow deltaic systems. The Gulf of Papua, on the south coast of the large island of New Guinea, is one such deltaic clinoform complex. It receives ∼4 Mt yr⁻¹ particulate terrestrial organic carbon with initial particle C_org loading ∼0.7 mg m⁻². C_org loading is reduced to ∼0.3 mg m⁻² in the topset-upper foreset zones of the delta despite additional inputs of mangrove and planktonic detritus, and high net sediment accumulation rates of 1-4 cm yr⁻¹. Carbon isotopic analyses (δ¹³C, Δ¹⁴C) of ΣCO₂ and C_org demonstrate rapid (<100 yr) remineralization of both terrestrial (δ¹³C <−28.6) and marine C_org (δ¹³C ∼−20.5) ranging in average age from modern (bomb) (Δ¹⁴C ∼60) to ∼1000 yr (Δ¹⁴C ∼−140). Efficient and rapid remineralization in the topset-upper foreset zone is promoted by frequent physical reworking, bioturbation, exposure, and reoxidation of deposits. The seafloor in these regions, particularly <20 m, apparently functions as a periodically mixed, suboxic batch reactor dominated by microbial biomass. Although terrestrial sources can be the primary metabolic substrates at inshore sites, relatively young marine C_org often preferentially dominates pore water ΣCO₂ relative to bulk C_org in the upper foreset. Thus a small quantity of young, rapidly recycled marine organic material is often superimposed on a generally older, less reactive terrestrial background. Whereas the pore water ΣCO₂ reflects both rapidly cycled marine and terrestrial sources, terrestrial material dominates the slower overall net loss of C_org from particles in the topset-upper foreset zone (i.e. recycled marine C_org leaves little residue). Preferential utilization of C_org subpools and diagenetic fractionation of C isotopes supports the reactive continuum model as a conceptual basis for net decomposition kinetics. Early diagenetic fractionation of C isotopes relative to the bulk sedimentary C_org composition can produce changes in ¹⁴C activity independent of radioactive decay. In the Gulf of Papua topset-upper foreset, Δ¹⁴C of pore water ΣCO₂ averaged ∼ 300‰ greater than C_org sediment between ∼1-3 m depth in deposits. Diagenetic fractionation and decomposition aging of sedimentary C_org compromises simple application of ¹⁴C for determination of sediment accumulation rates in diagenetically reactive deposits.     

Deformation microstructures in experimentally deformed Maryland diabase

Experimentally deformed Maryland diabase has been examined using the transmission electron microscope in order to determine the mechanisms of deformation operative over a range of temperatures and pressures and thereby aid in the interpretation of polyphase flow data. Deformation mechanisms within the plagioclase and clinopyroxene of the diabase have been compared to those within monomineralic aggregates of these phases deformed at the same conditions. Both phases deform by microfracturing, mechanical twinning, and intracrystalline slip.Data for the monomineralic aggregates show that plagioclase is stronger than clinopyroxene at <800°C, but weaker at ≥ 800°C, for a pressure of 15 kbar and strain rate of 10^?6/sec. Observations of the diabase are consistent with this result: at < 800°C, the plagioclase and pyroxene grains are about equally strained, whereas at ≥ 800°C, almost all of the sample strain is accommodated by the plagioclase, the more continuous phase.     

Radiolytic alteration of biopolymers in the Mulga Rock (Australia) uranium deposit

We investigated the effect of ionizing radiation on organic matter (OM) in the carbonaceous uranium (U) mineralization at the Mulga Rock deposit, Western Australia. Samples were collected from mineralized layers between 53 and 58.5 m depths in the Ambassador prospect, containing <5300 ppm U. Uranium bears a close spatial relationship with OM, mostly finely interspersed in the attrinite matrix and via enrichments within liptinitic phytoclasts (mainly sporinite and liptodetrinite). Geochemical analyses were conducted to: (i) identify the natural sources of molecular markers, (ii) recognize relationships between molecular markers and U concentrations and (iii) detect radiolysis effects on molecular marker distributions. Carbon to nitrogen ratios between 82 and 153, and Rock–Eval pyrolysis yields of 316–577 mg hydrocarbon/g TOC (HI) and 70–102 mg CO₂/g TOC (OI) indicate a predominantly lipid-rich terrigenous plant OM source deposited in a complex shallow swampy wetland or lacustrine environment. Saturated hydrocarbon and ketone fractions reveal molecular distributions co-varying with U concentration. In samples with <1700 ppm U concentrations, long-chain n-alkanes and alkanones (C₂₇–C₃₁) reveal an odd/even carbon preference indicative of extant lipids. Samples with ⩾1700 ppm concentrations contain intermediate-length n-alkanes and alkanones, bearing a keto-group in position 2–10, with no carbon number preference. Such changes in molecular distributions are inconsistent with diagenetic degradation of terrigenous OM in oxic depositional environments and cannot be associated with thermal breakdown due to the relatively low thermal maturity of the deposits (R_r = 0.26%). It is assumed that the intimate spatial association of high U concentrations resulted in breakdown via radiolytic cracking of recalcitrant polyaliphatic macromolecules (spores, pollen, cuticles, or algal cysts) yielding medium chain length n-alkanes (C₁₃–C₂₄). Reactions of n-alkenes with OH⁻ radicals from water hydrolysis produced alcohols that dehydrogenated to alkanones or through carbonylation formed alkanones. Rapid reactions with hydroxyl radicals likely decreased the isomerization of n-alkenes and decreased alkanone diversity, such that the alkan-2-one isomer is predominant. This specific distribution of components generated by natural radiolysis enables their application as “radiolytic molecular markers”. Breaking of C–C bonds through radiolytic cracking at temperatures much lower than the oil window (<50 °C) can have profound implications on initiation of petroleum formation, paleoenvironmental reconstructions, mineral exploration and in tracking radiolysis of OM.     

Diagenesis of plant biopolymers: Decay and macromolecular preservation of Metasequoia

Analysis of modern Metasequoia leaves revealed the presence of the structural polyester cutin, guaiacyl lignin units and polysaccharides. Analysis of environmentally decayed Metasequoia leaves revealed that guaiacyl lignin units and cellulose were degraded more than vinyl phenol (the last being the primary pyrolysis product of cutin and plant cuticles) suggesting that cutin is more stable than lignin and cellulose during degradation, contrary to some previous studies. This observation is supported by electron microscopy showing changes in the cellular structure and cuticle of modern, decayed and fossil Metasequoia leaves. Metasequoia fossils from the Eocene of Republic (Washington State) showed a significant aliphatic component, but biopolymeric lignin and polysaccharides were not detected. Fossils from the Eocene of Axel Heiberg revealed the presence of lignin and an aliphatic polymer up to C₂₉ with cellulose, and fossils from the Miocene Clarkia deposit (Idaho) revealed lignin and an aliphatic polymer up to C₂₇ without any polysaccharides. Modern Metasequoia needles heated experimentally in confined conditions generated a macromolecular composition with an aliphatic polymer up to C₃₂ and additional phenolic compounds similar to those present in the fossils. Experimental heating of cutin is known to generate an aliphatic polymer with carbon chain length units <C₂₀. Thus, the n-alkyl component with chain length units >C₂₀ in the heated Metasequoia needles is a product of incorporation of longer chain plant waxes, indicated by the odd/even predominance of the >C₂₇ n-alkanes. The resistant nature of cutin compared to lignin and polysaccharides explains the presence of an n-alkyl component (<C₂₀) in fossil leaves even when polysaccharides are absent and lignin has decayed; cutin and its diagenetically altered products contribute significantly to the presence of aliphatic components in terrestrially derived sedimentary organic matter.     

Limitations on the climatic and ecological signals provided by the δC values of phytoliths from a C4 North American prairie grass

Silica phytoliths, which are deposits of opal-A that precipitate in the intra- and intercellular spaces of plant tissues during transpiration, commonly contain small amounts of occluded organic matter. In this paper, we investigate whether the δ¹³C values of phytoliths from a C₄ grass, Calamovilfa longifolia, vary in response to climatic variables that can affect the carbon-isotope composition of plant tissues. There is no significant correlation (r² < 0.3) between climate variables and the δ¹³C values of C. longifolia tissues (average δ¹³C_tissue = −13.1 ± 0.6 ‰; n = 70) across the North American prairies. However, plant tissue δ¹³C values are lower for grasses collected in populated areas where the δ¹³C value of atmospheric CO₂ is expected to be lower because of fossil fuel burning. Phytolith δ¹³C values are more variable (δ¹³C = −27.3 to −23.0‰; average = −25.1 ± 1.3‰; n = 34) and more sensitive to changes in aridity than whole tissue δ¹³C values. The strongest correlations are obtained between the δ¹³C values of stem or sheath phytoliths and humidity (r² = 0.3), latitude (r² = 0.4) and amount of precipitation (r² = 0.5). However, use of these relationships is limited by the wide spread in δ¹³C values of phytoliths from different plant tissues at the same location. We have been unable to infer any relationship between δ¹³C values of phytoliths and expected variations in the δ¹³C values of atmospheric CO₂. The C. longifolia phytoliths are depleted of ¹³C relative to tissue carbon by 10-14‰. This means that the phytoliths examined in this study have carbon isotopic compositions within the range reported previously for phytoliths from C₃ plants. This observation may further limit the usefulness of soil-phytolith assemblage δ¹³C values for identifying shifts in grassland C₃:C₄ ratios.     

Assessing the factors controlling high sedimentation rates from the latest Barremian–earliest Aptian in the hemipelagic setting of the restricted Organyà Basin,NE Spain

The Organyà Basin, south–central Spanish Pyrenees, developed as a marginal depocenter during a rapid extensional phase of anticlockwise rotation of the Iberian plate. As a result of increased subsidence, an important change in sedimentation occurred from the late Barremian to the Aptian leading to unusually high sediment accumulation rates. Approximately 1000 m of hemipelagic marls and limestones accumulated during this time interval.Here we studied the basal 85 m of the hemipelagic facies of the El Pui section, Organyà Basin, that are characterized by alternating 15 cm – ∼3 m thick beds of limestone and marls. Geochemical analyses indicate high total inorganic carbon (TIC) values (average 70%) suggesting enhanced CaCO₃ production and deposition. SEM analyses of the samples indicate high abundance of calcareous nannofossils, which together with the absence of shallow water taxa characteristic of the Urgonian Carbonate platform of Organyà, and the lack of sedimentary facies attributable to carbonate platform components point to nannofossils as the main source for the elevated TIC. Organic-rich levels (total organic carbon (TOC) up to 1.74%) concurrent with positive excursions up to 2‰ in δ¹³C_org, imply enhanced preservation of organic matter (OM) in the basin. In addition, pronounced peaks of δ¹³C_org higher than the global average suggest superimposed local factors related to intensified ¹²C removal due to primary productivity. Biomarker analyses and the δ¹³C_org profile suggest an autochthonous origin of the OM from phytoplankton and possible additional contributions from microbial communities.X-ray diffraction (XRD) results attest for sustained terrestrial fluxes as the source of nutrients to the basin because of a 30% average non-carbonate bulk mineral content in the sediment. The non-carbonate fraction is dominated by quartz (average, 14%) whereas the clay mineral assemblages are characterized by high illite content (>73 relative%) with minor concentrations of kaolinite (<5%), illite /smectite mixed layers (<17%) and chlorite (<15%), consistent with a provenance from the Paleozoic metamorphic terranes adjacent to the Organyà Basin.The integrated results suggest a high sediment accumulation rate (5 cm/ky–7.5 cm/ky) and enhanced carbon burial during the latest Barremian–earliest Aptian in the hemipelagic setting of the El Pui section.     

Molecular dynamics simulation of the CH4 and CH4-H2O systems up to 10 GPa and 2573 K

Based on our previous study of the intermolecular potential for pure H₂O and the strict evaluation of the competitive potential models for pure CH₄ and the ab initio fitting potential surface across CH₄-H₂O molecules in this study, we carried out more than two thousand molecular dynamics simulations for the PVTx properties of pure CH₄ and the CH₄-H₂O mixtures up to 2573 K and 10 GPa. Comparison of 1941 simulations with experimental PVT data for pure CH₄ shows an average deviation of 0.96% and a maximum deviation of 2.82%. The comparison of the results of 519 simulations of the mixtures with the experimental measurements reveals that the PVTx properties of the CH₄-H₂O mixtures generally agree with the extensive experimental data with an average deviation of 0.83% and 4% in maximum, which is equivalent to the experimental uncertainty. Moreover, the maximum deviation between the experimental data and the simulation results decreases to about 2% as temperature and pressure increase, indicating that the high accuracy of the simulation is well retained in the high temperature and pressure region.After the validation of the simulation method and the intermolecular potential models, we systematically simulated the PVTx properties of this binary system from 673 K and 0.05 GPa to 2573 K and 10 GPa. In order to integrate all the simulation results and the experimental data for the calculation of thermodynamic properties, an equation of state (EOS) is developed for the CH₄-H₂O system covering 673-2573 K and 0.01-10 GPa. Isochores for compositions <4 mol% CH₄ up to 773 K and 600 MPa are also determined in this paper. The program for the EOS can be downloaded from www.geochem-model.org/programs.htm.     

Theoretical calculation of oxygen isotope fractionation factors in carbonate systems

Using established methods of statistical mechanical calculation and a recent compilation of vibrational frequency data, we have computed oxygen isotope reduced partition function ratios (β values) for a large number of carbonate minerals. The oxygen isotope β values of carbonates are inversely correlated to both the mass and radius of the cation bonded to the carbonate anion but neither correlation is good enough to be used as a precise and accurate predictor of β values. There is an approximately 0.6% relative increase in the β values of aragonite per 10 kbar increase in pressure. These estimates of the pressure effect on β values are broadly similar to those deduced previously for calcite using the methods of mineral physics. In comparing the β values of our study with those derived recently from first-principles lattice dynamics calculations, we find near-perfect agreement for calcite and witherite (<0.3% deviation), reasonable agreement for dolomite (<0.9% deviation) and somewhat poorer agreement for aragonite and magnesite (1.5-2% deviation). In the system for which we have the most robust constraints, CO₂-calcite, there is excellent agreement between our calculations and experimental data over a broad range of temperatures (0-900 °C). Similarly, there is good to excellent correspondence between calculation and experiment for most other low to moderate atomic mass carbonate minerals (aragonite to strontianite). The agreement is not as good for high atomic mass carbonates (witherite, cerussite, otavite). In the case of witherite and cerussite, the discrepancy may be due, in part, to our calculation methodology, which does not account for the effect of cation mass on the magnitude of vibrational frequency shifts associated with heavy isotope substitution. However, the calculations also reveal an incompatibility between the high- and low-temperature experimental datasets for witherite and cerussite. Specifically, the shapes of fractionation factor versus 1/T² curves in the calcite-witherite and calcite-cerussite systems do not conform to the robust constraints on the basic shape of these curves provided by theory. This suggests that either the high- or low-temperature datasets for both minerals is in error. Dolomite-calcite fractionation factors derived from our calculations fall within the wide range of fractionations for this system given by previous experimental and natural sample studies. However, our compilation of available low-temperature (25-80 °C) experimental data reveal an unusual temperature dependence of fractionations in this system; namely, the data indicate an increase in the magnitude of fractionations between dolomite (or proto-dolomite) and calcite with increasing temperature. Such a trend is incompatible with theory, which stipulates that fractionations between carbonate minerals must decrease monotonically with increasing temperature. We propose that the anomalous temperature dependence seen in the low-temperature experimental data reflect changes in the crystallinity and degree of cation ordering of the dolomite phase over this temperature interval and the effect these changes have on the vibrational frequencies of dolomite. Similar effects may be present in natural systems at low-temperature and must be considered in applying experimental or theoretical fractionation data to these systems. In nearly all cases, carbonate mineral-calcite fractionation factors given by the present calculations are in as good or better agreement with experimental data than are fractionations derived from semi-empirical bond strength methods.     

Distribution and diagenesis of organic compounds in JOIDES sediment from Gulf of Mexico and western Atlantic

Fifteen sediment samples were studied from five drill sites recovered by the ‘Glomar Challenger’ on Legs I and IV in the Gulf of Mexico and western Atlantic. This study concentrated on compounds derived from biogenic precursors, namely: (1) hydrocarbons, (2) fatty acids, (3) pigments and (4) amino acids.Carbon isotope (δC¹³) data (values < ? 26%, relative to PDB), long-chain n-alkyl hydrocarbons ( ?C₂₇7) with odd carbon numbered molecules dominating even carbon numbered species, and presence of perylene proved useful as possible indicators for terrigenous contributions to the organic matter in some samples. Apparently land-derived organic matter can be transported for distances over 1000 km into the ocean and their source still recognized.The study was primarily designed to investigate: (i) the sources of the organic matter present in the sediment, (ii) their stability with time of accumulation and (iii) the conditions necessary for in situ formation of new compounds.     

Light element geochemistry of the Apollo 16 site

Pronounced variations in abundances and isotopic compositions of some light elements in soils from the Apollo 16 site are interpreted in terms of differing degrees of solar wind exposure for an originally, and approximately, homogeneous regolith. Carbon abundances in soils are compatible with a model in which equilibrium is established, after 10⁴-10⁵ yr, between solar wind input and loss by H stripping. However, this model does not explain the observed C isotopic distribution, suggesting that other sources of C or other processes, or both, are also important. Carbon abundances in rocks from Apollo 16 are higher (average 40 ppm) than at other landing sites although their isotopic compositions, ?35 < δ¹³C < ?16%. PDB, are normal. Abundances of N and, to a less extent, He and H in soils correlate with C as does a fraction of metallic Fe attributed to in situ reduction of indigenous Fe²⁺ by solar wind H.Fillet soil 67461 apparently contains solar wind C and N in a relatively unfractionated form, yielding an upper limit to solar wind (δ¹³C of ?16%., PDB and a value of 3.4 for $\text{C}\text{N}$ in the solar wind.Sulfur at the Apollo 16 site represents a paradox in that, although abundances in soils are apparently controlled by local rock S contents, they also correlate, for all but one sample, with δ³⁴S, which itself is apparently controlled by surface exposure age. A complex lunar S cycle is suggested.     

Molecular evidence for recent land use change from a swampy environment to a pond (Lorraine,France)

Evidence of a changing environment in the catchment area of a small pond (Lansquenet, Lorraine, France) during the last millennium was provided by coupling palynology data and organic ratios [terrestrial to aquatic ratio: TAR_(HC); the C₂₉ vs. C₂₇ sterols, C₂₉/C_27(ST); average chain length, ACL and aquatic/macrophytes ratio, P_aq]. The depositional and alteration conditions of organic matter (OM) were provided by the 5α(H)-stanols/Δ⁵-sterols ratio. This study shows that quite simple organic ratios clearly allow identification of the different evolution steps of a watershed, from a swamp to the progressive settlement of a pond. During the swampy period, the C/N_(at) (ca. 11.1), TAR_(HC) (ca. 36.8)_, C₂₉/C_27(ST) (ca. 8.7) and P_aq (<0.3) show a high contribution of allochthonous OM associated with the presence of particular aquatic and mesohygrophilous species. A woody level dated to the XIIIth century reflects the period of the settlement of the pond in a more oxic environment [5α(H)-stanol/Δ⁵sterol ratio <0.2]. Then, the progressive increase in aquatic input and the development of submerged and floating macrophytes are evidenced by low C/N_(at) (<7.6), TAR_(HC) (ca. 2.7), C₂₉/C_27(ST) (ca. 2) and high P_aq (ca. 0.5), suggesting an increase in the water level and eutrophication of the pond. A second oxic event [5α(H)-stanols/Δ⁵sterols ratio averaging 0.16], associated with extensive OM degradation, corresponds to the most recent dredging in 2002 and reflects an important disturbance of sediments due to pond management.