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1.
Black carbon (BC) is an important residue of wildfires in boreal forests, but its characteristics depend on its formation conditions. The objective of this study was to characterize the chemical and physical properties of BC produced under controlled laboratory conditions, while mimicking a gradient of wildfire severity. We used fuels originating from mosses, ericaceous shrubs and spruce trees, as they constitute the major types available in boreal forests. We varied the maximum temperature (MT) from 75 to 800 °C, the duration of charring from 0.5 to 24 h and the abundance of O2. BC properties were analyzed using elemental analysis and proximate analysis, solid state 13C nuclear magnetic resonance (NMR) spectroscopy, scanning electron microscopy (SEM) and surface area (SA) analysis. MT was the most significant factor affecting both chemical and physical changes. Results from 13C NMR spectroscopy indicated that 350 °C was a threshold temperature, above which spectra became dominated by aromatic structures for all fuels. Charring duration affected BC composition at both low (250 °C for 12 h vs. 24 h) and high (600 °C for 0.5 h vs. 6 h) MT. The presence of O2 influenced BC composition mainly at low MT (250 °C) and resulted in accelerated alkyl C degradation, accompanied with a distinct decrease in yield. Results from the SA analysis and the SEM micrographs showed that fuel type influenced BC physical properties, with moss-derived BC presenting higher surface area and microporosity than BC of woody origin. 相似文献
2.
Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (δ18OH2O) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O2 and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ± 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate–water oxygen isotope fractionation, ε18OSO4–H2O, of ~ 3.8‰ for the anaerobic experiments. Aerobic oxidation produced apparent εSO4–H2O values (6.4‰) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O2 into sulfate. δ34SSO4 values are ~ 4‰ lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in δ34SSO4 of ~? 1.5 ± 0.2‰ was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions. 相似文献
3.
Predicting pyrogenic carbon (PyC) or biochar stability from its precursor properties is critical for evaluating and managing terrestrial C stocks. Transmission mode Fourier transform infrared spectroscopy (FTIR) spectroscopy was compared with proximate analysis data and H/C and O/C for predicting C mineralization. PyC produced at 7 different temperatures from 6 different feedstocks, in addition to the original feedstock materials, was incubated for 3 yr at 30 °C in a sand matrix. A C debt or credit ratio was calculated by comparing the C remaining in the incubated PyC sample (accounting for the measured C lost during initial PyC production) to the C remaining in the incubated original feedstock. A value > 1 indicates that more C remains in the PyC than in the original feedstock (credit), while a value < 1 indicates a debt. After 3 yr, PyC produced at 300 °C lost significantly more C than higher temperature PyC material, but significant differences in C loss between PyC produced at temperatures ⩾ 350 °C were not detectable. The best predictor of C loss was a multiple linear regression model using the fractional FTIR signals at 816, 1048, 1374, 1424, 1460, 1590, 1700 and 2925 cm−1 as parameters (R2 0.80, p < 0.0001). After 3 yr, the C debt or credit ratio reached values significantly > 1 for all corn PyC samples and some bull, dairy and poultry PyC samples, resulting in net C credit, while all pine and oak PyC samples remained in debt. This C debt or credit ratio reveals that, depending on the timeline of interest, producing relatively low temperature PyC with less initial C loss can result in greater C savings than producing higher temperature PyC, even though the C remaining after exposure to higher pyrolysis temperatures is more stable. 相似文献
4.
The Duolong district in central Tibet hosts a number of porphyry as well as high sulfidation epithermal copper–gold deposits and prospects, associated with voluminous calc-alkaline volcanism and plutonism. In this study, we present new geochronological, geochemical, isotopic and mineralogical data for both economically mineralized and barren porphyritic intrusions from the Duobuza and Naruo porphyry Cu–Au deposits. Zircon U–Pb analyses suggest the emplacement of economically mineralized granodiorite porphyry and barren granodiorite porphyry at Naruo deposit took place at 119.8 ± 1.4 Ma and 117.2 ± 0.5 Ma, respectively. Four molybdenite samples from the Naruo deposit yield an isochron Re–Os age of 119.5 ± 3.2 Ma, indicating mineralization occurred synchronously with the emplacement of the early granodiorite porphyry. At Duobuza deposit, the barren quartz diorite porphyry intruded at 119.5 ± 0.7 Ma, and two economically mineralized intrusions intruded at 118.5 ± 1.2 Ma (granodiorite porphyry) and 117.5 ± 1.2 Ma (quartz diorite porphyry), respectively. Petrographic investigations and geochemical data indicate that all of the porphyritic intrusions were oxidized, water rich, and subduction-related calc-alkaline magmas. Zircons from the porphyritic intrusions have a wide range in the εHf (0–11.1) indicating that they were sourced from mixing of mantle-derived mafic, and crust-derived felsic melts. Moreover, the variation of trace element content of plagioclase phenocrysts indicates that the magma chambers were recharged by mafic magmas.Comparison of the composition of amphibole phenocrysts indicates the porphyry copper–gold mineralization at Duolong was generated in magma chambers at low crystallization temperatures and pressures (754° to 791 °C, 59 M to 73 MPa, n = 8), and under highly oxidizing conditions (ΔNNO 2.2 to 2.7, n = 8). In contrast, barren intrusions were sourced from the magma chambers with higher crystallization temperatures and pressures (816° to 892 °C, 111 to 232 MPa, n = 22) that were less oxidizing (ΔNNO 0.6 to 1.6, n = 22). The requirement for a thermal contrast is supported by the declining of Ti content in magnetite crystals in barren intrusions (12,550 to 34,200 ppm) versus those from economically mineralized intrusions (600 to 3400 ppm). Moreover, the V content in magnetite crystals from economically mineralized intrusions (990 to 2510 ppm) is lower than those recorded from barren intrusions (2610 to 3510 ppm), which might reflect the variation in oxidation state of the magma. The calculated water solubility of the magma forming the economically mineralized intrusions (3.2–3.7 wt%) is lower than that of magma forming the barren intrusions (4.6–6.4 wt%). Based on the chemical–physical characteristics of economically mineralized magma, our study suggests that the development of porphyry Cu–Au mineralization at Duolong was initiated by shallow-level emplacement of a magma that crystallized at lower temperatures and pressures. Experimental studies show that copper and water solubilities in silicate melts decrease with falling temperatures and pressures, indicating metals and ore-forming fluids are more likely to be released from a magma reservoir emplaced at shallow crustal levels. We propose the magnetite might be a convenient exploration tool in the search for porphyry copper mineralization because the variations in Ti and V content of mineral concentrates and rock samples are indicative of barren versus mineralized intrusions. 相似文献
5.
The environmental conditions of the Szczecin Bay, which existed prior to Szczecin Lagoon, have been reconstructed on the basis of the stable carbon and oxygen isotope (18O and 13C) analysis and radiocarbon dates obtained for subfossil shells of Cerastoderma (Cardium) glaucum. The shells in the collected core were well preserved in their life positions, representing a geochemical record of past temperature variation over the middle Holocene. Three major periods with different thermal conditions have been distinguished in the interval ~ 6000–4300 cal yr BP, when the important Littorina regional transgression took place. During the first period, 6000–5250 cal yr BP, water temperature decreased by 1.4°C, and then remained constant over the second period (5250–4750 cal yr BP). In contrast, during the third period (4750–4300 cal yr BP) both δ-values were highly variable and the mean summer temperature (March–November) increased by about 3.5°C. During first two periods, δ18O and δ13C were significantly correlated, indicating stability of the environmental conditions. 相似文献
6.
《Applied Geochemistry》2006,21(7):1240-1247
This paper reports the abundance of elemental S in drain sediments associated with acid sulfate soils. The sediments exhibited near-neutral pH (5.97–7.27), high concentrations of pore-water Fe2+ (1.37–15.9 mM) and abundant oxalate-extractable Fe (up to 4300 μmol g−1). Maximum acid-volatile sulfide (AVS) concentrations in each sediment profile were high (118–1019 μmol g−1), with AVS often exceeding pyrite-S. Elemental S occurred at concentrations of 13–396 μmol g−1, with the higher concentrations exceeding previous concentrations reported for other sedimentary systems. Up to 62% of reduced inorganic S near the sediment/water interface was present as elemental S, due to reaction between AVS and oxidants such as O2 and Fe(III). Significant correlation (r = 0.74; P < 0.05) between elemental S and oxalate-extractable Fe(III) is indicative of elemental S formation by in situ oxidation of AVS. The results indicate that AVS oxidation in near-surface sediments is dynamic in acidified coastal floodplain drains, causing elemental S to be a quantitatively important intermediate S fraction. Transformations of elemental S may therefore strongly influence water quality in ASS landscapes. 相似文献
7.
Significant amounts of sulfuric acid (H2SO4) rich saline water can be produced by the oxidation of sulfide minerals contained in inland acid sulfate soils (IASS). In the absence of carbonate minerals, the dissolution of phyllosilicate minerals is one of very few processes that can provide long-term acid neutralisation. It is therefore important to understand the acid dissolution behavior of naturally occurring clay minerals from IASS under saline–acidic solutions. The objective of this study was to investigate the dissolution of a natural clay-rich sample under saline–acidic conditions (pH 1–4; ionic strengths = 0.01 and 0.25 M; 25 °C) and over a range of temperatures (25–45 °C; pH 1 and pH 4). The clay-rich sample referred to as Bottle Bend clay (BB clay) used was from an IASS (Bottle Bend lagoon) in south-western New South Wales (Australia) and contained smectite (40%), illite (27%), kaolinite (26%) and quartz (6%). Acid dissolution of the BB clay was initially rapid, as indicated by the fast release of cations (Si, Al, K, Fe, Mg). Relatively higher Al (pH 4) and K (pH 2–4) release was obtained from BB clay dissolution in higher ionic strength solutions compared to the lower ionic strength solutions. The steady state dissolution rate (as determined from Si, Al and Fe release rates; RSi, RAl, RFe) increased with decreasing solution pH and increasing temperature. For example, the highest log RSi value was obtained at pH 1 and 45 °C (−9.07 mol g−1 s−1), while the lowest log RSi value was obtained at pH 4 and 25 °C (−11.20 mol g−1 s−1). A comparison of these results with pure mineral dissolution rates from the literature suggests that the BB clay dissolved at a much faster rate compared to the pure mineral samples. Apparent activation energies calculated for the clay sample varied over the range 76.6 kJ mol−1 (pH 1) to 37.7 kJ mol−1 (pH 4) which compare very well with the activation energy values for acidic dissolution of monomineralic samples e.g. montmorillonite from previous studies. The acid neutralisation capacity (ANC) of the clay sample was calculated from the release of all structural cations except Si (i.e. Al, Fe, K, Mg). According to these calculations an ANC of 1.11 kg H2SO4/tonne clay/day was provided by clay dissolution at pH 1 (I = 0.25 M, 25 °C) compared to an ANC of 0.21 kg H2SO4/tonne clay/day at pH 4 (I = 0.25 M, 25 °C). The highest ANC of 6.91 kg H2SO4/tonne clay/day was provided by clay dissolution at pH 1 and at 45 °C (I = 0.25 M), which is more than three times higher than the ANC provided under the similar solution conditions at 25 °C. In wetlands with little solid phase buffering available apart from clay minerals, it is imperative to consider the potential ANC provided by the dissolution of abundantly occurring phyllosilicate minerals in devising rehabilitation schemes. 相似文献
8.
Three large-scale experimental waste rock piles (test piles) were constructed and instrumented at the Diavik Diamond Mine in the Northwest Territories, Canada, as part of an integrated field and laboratory study to measure and compare physical and geochemical characteristics of experimental, low sulfide waste rock piles at various scales. This paper describes the geochemical response during the first season from a test pile containing 0.053 wt.% S. Bulk drainage chemistry was measured at two sampling points for pH, Eh, alkalinity, dissolved cations and anions, and nutrients. The geochemical equilibrium model MINTEQA2 was used to interpret potential mineral solubility controls on water chemistry. The geochemical response characterizes the initial flushing response of blasting residues and oxidation products derived from sulfides in waste rock exposed to the atmosphere for less than 1 year. Sulfate concentrations reached 2000 mg L−1 when ambient temperatures were >10 °C, and decreased as ambient temperatures declined to <0 °C. The pH decreased to <5, concomitant with an alkalinity minimum of <1 mg L−1 (as total CaCO3), suggesting all available alkalinity is consumed by acid-neutralizing reactions. Concentrations of Al and Fe were <0.36 and <0.11 mg L−1, respectively. Trends of pH and alkalinity and the calculated saturation indices for Al and Fe (oxy)hydroxides suggest that dissolution of Al and Fe (oxy)hydroxide phases buffers the pH. The effluent water showed increased concentrations of dissolved Mn (<13 mg L−1), Ni (<7.0 mg L−1), Co (<1.5 mg L−1), Zn (<0.5 mg L−1), Cd (<0.008 mg L−1) and Cu (<0.05 mg L−1) as ambient temperatures increased. Manganese is released by aluminosilicate weathering, Ni and Co by pyrrhotite [Fe1−xS] oxidation, Zn and Cd by sphalerite oxidation, and Cu by chalcopyrite [CuFeS2] oxidation. No dissolved metals appear to have discrete secondary mineral controls. Changes in SO4, pH and metal concentrations indicate sulfide oxidation is occurring and effluent concentrations are influenced by ambient temperatures and, possibly, increasing flow path lengths that transport reaction products from previously unflushed waste rock. 相似文献
9.
A field experiment is being carried out at the Diavik diamond mine in northern Canada to investigate the influence of unsaturated flow behavior on the quality of drainage from mine waste rock piles in a region of continuous permafrost. This paper is part of a series describing processes affecting the weathering of waste rock and transport of reaction products at this site; here the focus is on unsaturated water flow and its role in mass loading. Two 15 m-high instrumented test piles have been built on 60 m by 50 m collection systems, each consisting of lysimeters and a large impermeable high-density polyethylene (HDPE) liner. Collection lysimeters are installed nearby to investigate infiltration in the upper 2 m of the waste rock. Porosity, water retention curves, and hydraulic conductivity functions are estimated from field measurements and for samples ranging in size from 200 cm3 to 16 m3. Net infiltration in 2007 is estimated to have been 37% of the rainfall for mean annual rainfall conditions. Early-season infiltration freezes and is remobilized as the waste rock thaws. Wetting fronts migrate at rates of 0.2–0.4 m d−1 in response to common rainfall events and up to 5 m d−1 in response to intense rainfall. Pore water and non-reactive solutes travel at rates of <10−2 to 3 × 10−2 m d−1 in response to common rainfall events and up to 0.7 m d−1 in response to intense rainfall. Time-varying SO4 mass loading from the base of the test piles is dictated primarily by the flow behavior, rather than by changes in solute concentrations. 相似文献
10.
《Applied Geochemistry》2006,21(8):1347-1361
The relationships between factors that control subsurface flow and the timing, duration, and intensity of acidity generation and leaching of metals from waste-rock dumps are investigated. A 12 m high waste-rock pile that had been constructed in 1994 at Key Lake, Saskatchewan, Canada was disassembled, sampled and characterized in 2000. Physical properties that control water flow were characterized by measuring soil–water suction, volumetric water content, and the grain-size distribution at 60 randomized sites within the pile. Grain-size distribution was also measured at an additional 20 grid locations within the pile. Paste pH, pore-water geochemistry, mineralogy, and water-soluble extractions were used to investigate geochemical processes and sulfide oxidation at each of the 20 grid locations. A field-based soil–water characteristic curve could not be developed from the spatially variable and hysteretic field data; consequently, the grain-size distribution was used as a relative measure of subsurface flow and of the tendency to contain water under unsaturated conditions. The geochemical characterization demonstrated that marcasite underwent preferential weathering relative to pyrite and chalcopyrite, that dolomite was the main buffering carbonate mineral, and that gypsum, jarosite, and Fe oxyhydroxides were the main secondary (supergene) minerals. The pore waters contained up to 78,000 mg L−1 SO4, 690 mg L−1 Ni and 1400 mg L−1 U (800, 11.7 and 6 mM, respectively), suggesting that significant weathering had occurred. The pore water chemistry varied considerably between sampling sites. However, neither a correlation of pore-water chemistry with grain-size distribution nor a spatial relationship within the sampled grid was discernible. 相似文献
11.
Shells of the helicid Cepaea nemoralis were studied using taphonomic, isotopic and morphometric measurements to estimate late glacial–Holocene (~ 12.1–6.3 cal ka BP) environmental conditions in northern Spain. Higher taphonomic alteration among Holocene shells suggests lower sedimentation rates or higher shell-destruction rates than during glacial conditions. Shells preserved the aragonitic composition despite differing degree of skeleton damage. Shell δ13C values were ? 10.3 ± 1.1‰, ? 8.2 ± 2.3‰, and ? 7.3 ± 1.6‰ for modern, Holocene and late-glacial individuals, respectively. Higher δ13C values during the late-glacial and some Holocene periods imply higher water stress of C3 plants and/or higher limestone contribution than today. Intrashell δ13C values were higher during juvenile stages suggesting higher limestone ingestion to promote shell growth. Shell δ18O values were ? 1.1 ± 0.7‰, ? 0.9 ± 0.8‰ and ? 0.1 ± 0.7‰ for modern, Holocene and late-glacial specimens, respectively. A snail flux-balance model suggests that during ~ 12.1 ? 10.9 cal ka BP conditions were drier and became wetter at ~ 8.4 ? 6.3 cal ka BP and today. Intrashell δ18O profiles reveal that glacial individuals experienced more extreme seasonality than interglacial shells, despite possible larger hibernation periods. Shell size correlated positively with δ18O values, suggesting that growth rates and ultimate adult size of C. nemoralis may respond to climate fluctuation in northern Spain. 相似文献
12.
Primary ore-forming minerals retain geochemical signatures of magmatic crystallization information and can reveal the petrochemical conditions prevalent at the time of their formation. The Baogutu deposit is a typical reduced porphyry Cu deposit. Amphibole and biotite Fe3+/ΣFe ratios, minerals (feldspar, biotite, amphibole, zircon and apatite), in situ elemental and apatite Nd isotopic compositions were determined by Mössbauer spectroscopy, electron probe microanalysis, and laser ablation multiple-collection inductively coupled plasma mass spectrometry, respectively, to investigate the magma oxidation state, petrogenesis, source features, and to constrain the carbon species at magmatic stages for the intrusive phases. The results show that the primary plagioclase and amphibole in the mineralized diorite to granodiorite porphyry and post ore hornblende diorite porphyry are distinct (An26-55 versus An60-69; Mg-hornblende versus tschermakite). In particular, the amphibole shows distinct major and trace element compositions with light rare earth element enrichments and negative Eu anomalies in Mg-hornblende and light rare earth element depletions and no Eu anomalies in tschermakite. All the analyzed biotites are primary igneous phases with a biotite phenocryst profile showing significant variations of Zn, Cr, Sc and Sr from core to rim. These results may indicate the occurrence of mixing between two distinct magmas during mineral formation. Titanium in zircon and Si1 in amphibole thermometries indicate that magma crystallized at >900 °C and continued to ∼650 °C. In situ apatite Nd isotope (εNd(t) = 5.6–7.6, TDM2 = 620–460 Ma), indicate absence of significant reduced sedimentary contamination and the source of juvenile lower crust. Slightly decreasing Fe3+/ΣFe ratios from biotite and amphibole to whole rock indicate decreasing oxygen fugacity during magma crystallization. Recalculated biotite compositions according to Fe3+/ΣFe ratios indicate fO2 values of less than Ni-NiO buffer (NNO) which show slightly lower values than that estimated according to zircon/melt distribution coefficients Ce anomalies (∼ΔNNO + 0.6). These values are consistent with the features of reduced porphyry Cu deposits. Crystallization of other mineral phases significantly affects the reliability of oxybarometer of zircon/melt distribution coefficients Eu anomalies and Mn contents in apatite. This oxidation state suggests that only CO2 was present at the magmatic stage, and implies that CH4 formed during CO2 reduction occurring later hydrothermal alteration. The alteration of primary amphibole to actinolite released Ti, Al, Fe, Mn, Na and K to the fluid with later precipitation of titanite, albite and minor ilmenite and magnetite during actinolite alteration. 相似文献
13.
Phosphorite from the Meade Peak Phosphatic Shale member of the Permian Phosphoria Formation has been mined in southeastern Idaho since 1906. Dumps of waste rock from mining operations contain high concentrations of Se which readily leach into nearby streams and wetlands. While the most common mineralogical residence of Se in the phosphatic shale is elemental Se, Se(0), Se is also an integral component of sulfide phases (pyrite, sphalerite and vaesite–pyritess) in the waste rock. It may also be present as adsorbed selenate and/or selenite, and FeSe2 and organo-selenides.Se release from the waste rock has been observed in field and laboratory experiments. Release rates calculated from waste rock dump and column leachate solutions describe the net, overall Se release from all of the possible sources of Se listed above. In field studies, Se concentration in seepage water (pH 7.4–7.8) from the Wooley Valley Unit 4 dump ranges from 3600 µg/L in May to 10 µg/L by Sept. Surface water flow, Q, from the seep also declines over the summer, from 2 L/s in May to 0.03 L/s in Sept. Se flux ([Se] ? Q) reaches a steady-state of < 150 mg/day in 1–4 months, depending upon the volume of Q. Se release (mg/L) follows a first order reaction with a rate constant, k, = 1.35 – 6.35e?3 h? 1 (11.8–55.6 yr? 1).Laboratory experiments were performed with the waste shale in packed bed reactors; residence time varied from 0.09 to 400 h and outlet pH ～ 7.5. Here, Se concentration increased with increasing residence time and release was modeled with a first order reaction with k = 2.19e?3 h? 1 (19.2 yr? 1).Rate constants reported here fall within an order of magnitude of reported rate constants for oxidation of Se(0) formed by bacterial precipitation. This similarity among rate constants from both field and laboratory studies combined with the direct observation of Se(0) in waste shales of the Phosphoria Formation suggests that oxidation of Se(0) may control steady-state Se concentration in water draining the Wooley Valley waste dump. 相似文献
14.
Hong Lu Tengshui Chen Kliti Grice Paul Greenwood Ping’an Peng Guoying Sheng 《Organic Geochemistry》2009,40(8):902-911
An unusual series of C22–C27 monounsaturated sterenes and C24–C30 tetracyclic terpanes (17,21-secohopanes) were detected in relatively high concentrations in an immature evaporitic marl sediment of the Jinxian Sag, Bohai Bay Basin, North China. The site of unsaturation in these novel sterenes is assigned tentatively to the D ring on the basis of mass spectral interpretation, which also distinguishes them from reported unsaturated sterenes. Other hydrocarbon biomarker or stable isotope characteristics are indicative of microbial (e.g. methyl hopanes), phytoplankton or higher plant (depleted δ13C values of isoprenoids and hopanes) inputs and an anoxic carbonate depositional environment (hexacyclic hopanes; tetracyclic terpanes). The hydrocarbon composition showed no obvious biodegradation and the relatively high concentration of unsaturated terpenoids (e.g. gammacerene) and low values of other established maturity parameters (Ts/Tm = 0.23; Ro = 0.44%; Tmax = 417 °C), are consistent with sediments of low maturity. The novel, low molecular weight sterenes and the tetracyclic terpanes may be early diagenetic products of microbial sources in a carbonate environment. 相似文献
15.
The linkage between the iron and the carbon cycles is of paramount importance to understand and quantify the effect of increased CO2 concentrations in natural waters on the mobility of iron and associated trace elements. In this context, we have quantified the thermodynamic stability of mixed Fe(III) hydroxo-carbonate complexes and their effect on the solubility of Fe(III) oxihydroxides. We present the results of carefully performed solubility measurements of 2-line ferrihydrite in the slightly acidic to neutral–alkaline pH ranges (3.8–8.7) under constant pCO2 varying between (0.982–98.154 kPa) at 25 °C.The outcome of the work indicates the predominance of two Fe(III) hydroxo carbonate complexes FeOHCO3 and Fe(CO3)33−, with formation constants log*β°1,1,1 = 10.76 ± 0.38 and log β°1,0,3 = 24.24 ± 0.42, respectively.The solubility constant for the ferrihydrite used in this study was determined in acid conditions (pH: 1.8–3.2) in the absence of CO2 and at T = (25 ± 1) °C, as log*Ks,0 = 1.19 ± 0.41.The relative stability of the Fe(III)-carbonate complexes in alkaline pH conditions has implications for the solubility of Fe(III) in CO2-rich environments and the subsequent mobilisation of associated trace metals that will be explored in subsequent papers. 相似文献
16.
Y.B. Melnichenko A.P. Radlinski M. Mastalerz G. Cheng J. Rupp 《International Journal of Coal Geology》2009,77(1-2):69-79
Small angle neutron scattering techniques have been applied to investigate the phase behavior of CO2 injected into coal and possible changes in the coal pore structure that may result from this injection. Three coals were selected for this study: the Seelyville coal from the Illinois Basin (Ro = 0.53%), Baralaba coal from the Bowen Basin (Ro = 0.67%), and Bulli 4 coal from the Sydney Basin (Ro = 1.42%). The coals were selected from different depths to represent the range of the underground CO2 conditions (from subcritical to supercritical) which may be realized in the deep subsurface environment. The experiments were conducted in a high pressure cell and CO2 was injected under a range of pressure conditions, including those corresponding to in-situ hydrostatic subsurface conditions for each coal. Our experiments indicate that the porous matrix of all coals remains essentially unchanged after exposure to CO2 at pressures up to 200 bar (1 bar = 105 Pa). Each coal responds differently to the CO2 exposure and this response appears to be different in pores of various sizes within the same coal. For the Seelyville coal at reservoir conditions (16 °C, 50 bar), CO2 condenses from a gas into liquid, which leads to increased average fluid density in the pores (ρpore) with sizes (r) 1 × 105 ≥ r ≥ 1 × 104 Å (ρpore ≈ 0.489 g/cm3) as well as in small pores with size between 30 and 300 Å (ρpore ≈ 0.671 g/cm3). These values are by a factor of three to four higher than the density of bulk CO2 (ρCO2) under similar thermodynamic conditions (ρCO2 ≈ 0.15 g/cm3). At the same time, in the intermediate size pores with r ≈ 1000 Å the average fluid density is similar to the density of bulk fluid, which indicates that adsorption does not occur in these pores. At in situ conditions for the Baralaba coal (35 OC, 100 bar), the average fluid density of CO2 in all pores is lower than that of the bulk fluid (ρpore / ρCO2 ≈ 0.6). Neutron scattering from the Bulli 4 coal did not show any significant variation with pressure, a phenomenon which we assign to the extremely small amount of porosity of this coal in the pore size range between 35 and 100,000 Å. 相似文献
17.
《Applied Geochemistry》2005,20(1):23-39
Hydrothermal alteration at Los Azufres geothermal field is mostly propylitic with a progressive dehydration with depth and temperature increase. Argillic and advanced argillic zones overlie the propylitic zone owing to the activity of gases in the system. The deepest fluid inclusions (proto-fluid) are liquid-rich with low salinity, with NaCl dominant fluid type and ice melting temperatures (Tmi) near zero (0 °C), and salinities of 0.8 wt% NaCl equivalent. The homogenization temperature (Th) = 325 ± 5 °C. The boiling zone shows Th = ±300 °C and apparent salinities between 1 and 4.9 wt% NaCl equivalent, implying a vaporization process and a very important participation of non-condensable gases (NCGs), mostly CO2. Positive clathrate melting temperatures (fusion) with Th = 150 °C are observed in the upper part of the geothermal reservoir (from 0 to 700 m depth). These could well be the evidence of a high gas concentration. The current water produced at the geothermal wells is NaCl rich (geothermal brine) and is fully equilibrated with the host rock at temperatures between T = 300 and 340 °C. The hot spring waters are acid-sulfate, indicating that they are derived from meteoric water heated by geothermal steam. The NCGs related to the steam dominant zone are composed mostly of CO2 (80–98% of all the gases). The gases represent between 2 and 9 wt% of the total mass of the fluid of the reservoir.The authors interpret the evolution of this system as deep liquid water boiling when ascending through fractures connected to the surface. Boiling is caused by a drop of pressure, which favors an increase in the steam phase within the brine ascending towards the surface. During this ascent, the fluid becomes steam-dominant in the shallowest zone, and mixes with meteoric water in perched aquifers. Stable isotope compositions (δ18O–δD) of the geothermal brine indicate mixing between meteoric water and a minor magmatic component. The enrichment in δ18O is due to the rock–water interaction at relatively high temperatures. δ13C stable isotope data show a magmatic source with a minor meteoric contribution for CO2. The initial isotopic value δ34SRES = −2.3‰, which implies a magmatic source. More negative values are observed for shallow pyrite and range from δ34S (FeS2) = −4‰ to −4.9‰, indicating boiling. The same fractionation tendencies are observed for fluids in the reservoir from results for δ18O. 相似文献
18.
Carbon isotope ratio (δ13C) values of lipid biomarkers from plants can be used to assess water use efficiency and to reconstruct environmental conditions in the past. We assessed the effect of salinity on the δ13C values for leaf wax n-C31 and n-C33 alkanes, bulk leaf matter and leaf total lipid extracts from Avicennia marina (gray mangrove) trees growing along the Brisbane River estuary in Queensland, Australia. We observed an increase in 0.19 ± 0.053‰ (R2 0.61, p 0.008) and 0.16 ± 0.052‰ (R2 0.55, p 0.01) per salinity unit for the two n-alkanes, respectively, and of 0.087 ± 0.028‰ (R2 0.41, p 0.009) for whole leaves per salinity unit, indicating that water use efficiency of A. marina increased with the salt content of water. There was no correlation between δ13C values of total lipid extracts and salinity, perhaps because of a decrease in lipid concentration at higher salinity or because of varying contributions of different lipid classes to the extract. The robust relationship between salinity and δ13C values of leaf wax lipids provides a means of quantitatively reconstructing past salinity from carbon isotope ratios of mangrove lipid biomarkers in sediments. When paired with measurements of the hydrogen isotope ratio values of the same compounds, the approach should facilitate quantitative reconstruction of the hydrogen isotope composition of environmental water. In order for the method to successfully reconstruct past salinity and water isotopes, a mangrove source for leaf wax would need to be confirmed by palynological or other evidence, or the isotopic composition of a more source specific biomarker, such as taraxerol, would need to be measured. 相似文献
19.
Narraguinnep Reservoir in southwestern Colorado is one of several water bodies in Colorado with a mercury (Hg) advisory as Hg in fish tissue exceed the 0.3 μg/g guideline to protect human health recommended by the State of Colorado. Concentrations of Hg and methyl-Hg were measured in reservoir bottom sediment and pore water extracted from this sediment. Rates of Hg methylation and methyl-Hg demethylation were also measured in reservoir bottom sediment. The objective of this study was to evaluate potential sources of Hg in the region and evaluate the potential of reservoir sediment to generate methyl-Hg, a human neurotoxin and the dominant form of Hg in fish. Concentrations of Hg (ranged from 1.1 to 5.8 ng/L, n = 15) and methyl-Hg (ranged from 0.05 to 0.14 ng/L, n = 15) in pore water generally were highest at the sediment/water interface, and overall, Hg correlated with methyl-Hg in pore water (R2 = 0.60, p = 0007, n = 15). Net Hg methylation flux in the top 3 cm of reservoir bottom sediment varied from 0.08 to 0.56 ng/m2/day (mean = 0.28 ng/m2/day, n = 5), which corresponded to an overall methyl-Hg production for the entire reservoir of 0.53 g/year. No significant point sources of Hg contamination are known to this reservoir or its supply waters, although several coal-fired power plants in the region emit Hg-bearing particulates. Narraguinnep Reservoir is located about 80 km downwind from two of the largest power plants, which together emit about 950 kg-Hg/year. Magnetic minerals separated from reservoir sediment contained spherical magnetite-bearing particles characteristic of coal-fired electric power plant fly ash. The presence of fly-ash magnetite in post-1970 sediment from Narraguinnep Reservoir indicates that the likely source of Hg to the catchment basin for this reservoir has been from airborne emissions from power plants, most of which began operation in the late-1960s and early 1970s in this region. 相似文献
20.
《Chemie der Erde / Geochemistry》2015,75(1):65-72
This study was conducted on recent desert samples—including (1) soils, (2) plants, (3) the shell, and (4) organic matter from modern specimens of the land snail Eremina desertorum—which were collected at several altitudes (316–360 m above sea level) from a site in the New Cairo Petrified Forest. The soils and shellE. desertorum were analyzed for carbonate composition and isotopic composition (δ18O, δ13C). The plants and organic matterE. desertorum were analyzed for organic carbon content and δ13C. The soil carbonate, consisting of calcite plus minor dolomite, has δ18O values from −3.19 to −1.78‰ and δ13C values −1.79 to −0.27‰; covariance between the two values accords with arid climatic conditions. The local plants include C3 and C4 types, with the latter being dominant. Each type has distinctive bulk organic carbon δ13C values: −26.51 to −25.36‰ for C3-type, and −13.74 to −12.43‰ for C4-type plants.The carbonate of the shellE. desertorum is composed of aragonite plus minor calcite, with relatively homogenous isotopic compositions (δ18Omean = −0.28 ± 0.22‰; δ13Cmean = −4.46 ± 0.58‰). Most of the δ18O values (based on a model for oxygen isotope fractionation in an aragonite-water system) are consistent with evaporated water signatures. The organic matterE. desertorum varies only slightly in bulk organic carbon δ13C values (−21.78 ± 1.20‰) and these values suggest that the snail consumed more of C3-type than C4-type plants. The overall offset in δ13C values (−17.32‰) observed between shellE. desertorum carbonate and organic matterE. desertorum exceeds the value expected for vegetation input, and implies that 30% of carbon in the shellE. desertorum carbonate comes from the consumption of limestone material. 相似文献