Geochemical fluxes and weathering of volcanic terrains on high standing islands: Taranaki and Manawatu-Wanganui regions of New Zealand     

Steven T. Goldsmith  Anne E. Carey  W. Berry Lyons  D. Murray Hicks 《Geochimica et cosmochimica acta》2008,72(9):2248-2267

Sediment fluxes from high standing oceanic islands (HSIs) such as New Zealand are some of the highest known [Milliman J. D. and Syvitski J. P. M. (1992) Geomorphic/tectonic control of sediment discharge to the ocean: the importance of small mountainous rivers. J. Geol.100, 525-544]. Recent geochemical work has suggested that along with their extremely high physical weathering yields, many New Zealand watersheds also have very high chemical weathering yields. In New Zealand, the magnitude of both the physical and chemical weathering yields is related to the lithology of the watershed. Most of the previous work on this topic has been undertaken in Southern Alps watersheds of schist and greywacke and in East Cape watersheds of semi-consolidated marine sediments and greywacke. We recently sampled North Island watersheds in the Taranaki and Manawatu-Wanganui regions which have been subjected to volcanism since the Miocene. We sampled watersheds that contain both volcanic and sedimentary rocks. A series of water and sediment samples was collected and analyzed for major, minor and trace elements. This was done to quantify the weathering intensities in the watersheds and to establish the relationship between physical and chemical weathering yields in volcanic lithologies. Our results reveal distinct chemical signatures for the different regions. Waters draining the Taranaki region volcanics are significantly enriched in K⁺, and depleted in Ca²⁺ and Sr²⁺ compared to waters draining the Manawatu-Wanganui region volcanics, which also traverse expanses of sedimentary siltstones and mudstones. The Ca²⁺ and Sr²⁺ depletions may reflect the relative absence of CaCO₃ in the Taranaki region watersheds. In addition, sediment samples from the Taranaki region show significant enrichment in Ti, Al, Ca, Fe, Mn, Mg, Ca, and P and depletion in Si and Rb compared to those of the Manawatu-Wanganui region. From total dissolved solids concentrations and mean annual water discharge, we calculate chemical weathering yields of 60-240 tons km⁻² a⁻¹. These weathering yields fall within the middle to upper range of those previously documented for the Southern Alps (93-480 tons km⁻² a⁻¹) and East Cape (62-400 tons km⁻² a⁻¹). Calculated silicate weathering yields of 12-33.6 tons km⁻² a⁻¹ and CO₂ consumption of 852-2390 × 10³ mol km⁻² a⁻¹ for the rivers draining the Taranaki volcanic region are higher than those previously reported for watersheds hosted in sedimentary and metamorphosed rock terrains on HSIs. CO₂ consumption is found to be within the range previously measured for the basaltic terrains of the Deccan Traps (580-2450 × 10³ mol km⁻² a⁻¹) and Réunion Island(1300-4400 × 10³ mol km⁻² a⁻¹). Our calculated chemical weathering yields demonstrate the importance of HSIs, particularly those with volcanic terrains, when considering global geochemical fluxes.  相似文献   

Stream geochemistry, chemical weathering and CO₂ consumption potential of andesitic terrains, Dominica, Lesser Antilles     

Steven T. Goldsmith  Anne E. Carey  Brent M. Johnson  Susan A. Welch  William H. McDowell 《Geochimica et cosmochimica acta》2010,74(1):85-7854

Recent studies of chemical weathering of andesitic-dacitic material on high-standing islands (HSIs) have shown these terrains have some of the highest observed rates of chemical weathering and associated CO₂ consumption yet reported. However, the paucity of stream gauge data in many of these terrains has limited determination of chemical weathering product fluxes. In July 2006 and March 2008, stream water samples were collected and manual stream gauging was performed in watersheds throughout the volcanic island of Dominica in the Lesser Antilles. Distinct wet and dry season solute concentrations reveal the importance of seasonal variations on the weathering signal. A cluster analysis of the stream geochemical data shows the importance of parent material age on the overall delivery of solutes. Observed Ca:Na, HCO₃:Na and Mg:Na ratios suggest crystallinity of the parent material may also play an important role in determining weathering fluxes. From total dissolved solids concentrations and mean annual discharge calculations we calculate chemical weathering yields of (6-106 t km⁻² a⁻¹), which are similar to those previously determined for basalt terrains. Silicate fluxes (3.1-55.4 t km⁻² a⁻¹) and associated CO₂ consumption (190-1575 × 10³ mol km⁻² a⁻¹) determined from our study are among the highest determined to date. The calculated chemical fluxes from our study confirm the weathering potential of andesitic-dacitic terrains and that additional studies of these terrains are warranted.  相似文献   

Tracing nitrogen in volcanic and geothermal volatiles from the Nicaraguan volcanic front     

L.J. Elkins  T.P. Fischer  Z.D. Sharp  J. Walker 《Geochimica et cosmochimica acta》2006,70(20):5215-5235

We report new chemical and isotopic data from 26 volcanic and geothermal gases, vapor condensates, and thermal water samples, collected along the Nicaraguan volcanic front. The samples were analyzed for chemical abundances and stable isotope compositions, with a focus on nitrogen abundances and isotope ratios. These data are used to evaluate samples for volatile contributions from magma, air, air-saturated water, and the crust. Samples devoid of crustal contamination (based upon He isotope composition) but slightly contaminated by air or air-saturated water are corrected using N₂/Ar ratios in order to obtain primary magmatic values, composed of contributions from upper mantle and subducted hemipelagic sediment on the down-going plate. Using a mantle endmember with δ¹⁵N = −5‰ and N₂/He = 100 and a subducted sediment component with δ¹⁵N = +7‰ and N₂/He = 10,500, the average sediment contribution to Nicaraguan volcanic and geothermal gases was determined to be 71%. Most of the gases were dominated by sediment-derived nitrogen, but gas from Volcán Mombacho, the southernmost sampling location, had a mantle signature (46% from subducted sediment, or 54% from the mantle) and an affinity with mantle-dominated gases discharging from Costa Rica localities to the south. High CO₂/N_{2 exc.} ratios (N_{2 exc.} is the N₂ abundance corrected for contributions from air) in the south are similar to those in Costa Rica, and reflect the predominant mantle wedge input, whereas low ratios in the north indicate contribution by altered oceanic crust and/or preferential release of nitrogen over carbon from the subducting slab. Sediment-derived nitrogen fluxes at the Nicaraguan volcanic front, estimated by three methods, are 7.8 × 10⁸ mol N/a from ³He flux, 6.9 × 10⁸ mol/a from SO₂ flux, and 2.1 × 10⁸ and 1.3 × 10⁹ mol/a from CO₂ fluxes calculated from ³He and SO₂, respectively. These flux results are higher than previous estimates for Central America, reflecting the high sediment-derived volatile contribution and the high nitrogen content of geothermal and volcanic gases in Nicaragua. The fluxes are also similar to but higher than estimated hemipelagic nitrogen inputs at the trench, suggesting addition of N from altered oceanic basement is needed to satisfy these flux estimates. The similarity of the calculated input of N via the trench to our calculated outputs suggests that little or none of the subducted nitrogen is being recycled into the deeper mantle, and that it is, instead, returned to the surface via arc volcanism.  相似文献   

Diffuse gas emissions at the Ukinrek Maars,Alaska: Implications for magmatic degassing and volcanic monitoring     

William C. Evans  Deborah Bergfeld  Robert G. McGimsey  Andrew G. Hunt 《Applied Geochemistry》2009

Diffuse CO₂ efflux near the Ukinrek Maars, two small volcanic craters that formed in 1977 in a remote part of the Alaska Peninsula, was investigated using accumulation chamber measurements. High CO₂ efflux, in many places exceeding 1000 g m⁻² d⁻¹, was found in conspicuous zones of plant damage or kill that cover 30,000–50,000 m² in area. Total diffuse CO₂ emission was estimated at 21–44 t d⁻¹. Gas vents 3-km away at The Gas Rocks produce 0.5 t d⁻¹ of CO₂ that probably derives from the Ukinrek Maars basalt based on similar δ¹³C values (∼−6‰), ³He/⁴He ratios (5.9–7.2 R_A), and CO₂/³He ratios (1–2 × 10⁹) in the two areas. A lower ³He/⁴He ratio (2.7 R_A) and much higher CO₂/³He ratio (9 × 10¹⁰) in gas from the nearest arc-front volcanic center (Mount Peulik/Ugashik) provide a useful comparison. The large diffuse CO₂ emission at Ukinrek has important implications for magmatic degassing, subsurface gas transport, and local toxicity hazards. Gas–water–rock interactions play a major role in the location, magnitude and chemistry of the emissions.  相似文献   

Water geochemistry of the Xijiang basin rivers,South China: Chemical weathering and CO₂ consumption   总被引：1，自引：0，他引：1  

Zhifang Xu  Cong-Qiang Liu 《Applied Geochemistry》2010

  相似文献   

Transport and thermodynamics constrain belowground carbon turnover in a northern peatland     

Julia Beer 《Geochimica et cosmochimica acta》2007,71(12):2989-3002

Rates of anaerobic respiration are of central importance for the long-term burial of carbon (C) in peatlands, which are a relevant sink in the global C cycle. To identify constraints on anaerobic peat decomposition, we determined detailed concentration depth profiles of decomposition end-products, i.e. methane (CH₄) and dissolved inorganic carbon (DIC), along with concentrations of relevant decomposition intermediates at an ombrotrophic Canadian peat bog. The magnitude of in situ net production rates of DIC and CH₄ was estimated by inverse pore-water modeling. Vertical transport in the peat was slow and dominated by diffusion leading to the buildup of DIC and CH₄ with depth (5500 μmol L⁻¹ DIC, 500 μmol L⁻¹ CH₄). Highest DIC and CH₄ production rates occurred close to the water table (decomposition constant k_d ∼ 10⁻³-10⁻⁴ a⁻¹) or in some distinct zones at depth (k_d ∼ 10⁻⁴ a⁻¹). Deeper into the peat, decomposition proceeded very slowly at about k_d = 10⁻⁷ a⁻¹. This pattern could be related to thermodynamic and transport constraints. The accumulation of metabolic end-products diminished in situ energy yields of acetoclastic methanogenesis to the threshold for microbially mediated processes (−20 to −25 kJ mol⁻¹ CH₄). The methanogenic precursor acetate also accumulated (150 μmol L⁻¹). In line with these findings, CH₄ was formed by hydrogenotrophic methanogenesis at Gibbs free energies of −35 to −40 kJ mol⁻¹ CH₄. This was indicated by an isotopic fractionation α_CO2-CH4 of 1.069-1.079. Fermentative degradation of acetate, propionate and butyrate attained Gibbs free energies close to 0 kJ mol⁻¹ substrate. Although methanogenesis was apparently limited by some other factor in some peat layers, transport and thermodynamic constraints likely impeded respiratory processes in the deeper peat. Constraints on the removal of DIC and CH₄ may thus slow decomposition and contribute to the sustained burial of C in northern peatlands.  相似文献   

Solubility of nanocrystalline scorodite and amorphous ferric arsenate: Implications for stabilization of arsenic in mine wastes     

D. Paktunc  K. Bruggeman 《Applied Geochemistry》2010

Solubility experiments were performed on nanocrystalline scorodite and amorphous ferric arsenate. Nanocrystalline scorodite occurs as stubby prismatic crystals measuring about 50 nm and having a specific surface area of 39.88 ± 0.07 m²/g whereas ferric arsenate is amorphous and occurs as aggregated clusters measuring about 50–100 nm with a specific surface area of 17.95 ± 0.19 m²/g. Similar to its crystalline counterpart, nanocrystalline scorodite has a solubility of about 0.25 mg/L at around pH 3–4 but has increased solubilities at low and high pH (i.e. <2 and >6). Nanocrystalline scorodite dissolves incongruently at about pH > 2.5 whereas ferric arsenate dissolution is incongruent at all the pH ranges tested (pH 2–5). It appears that the solubility of scorodite is not influenced by particle size. The dissolution rate of nanocrystalline scorodite is 2.64 × 10⁻¹⁰ mol m⁻² s⁻¹ at pH 1 and 3.25 × 10⁻¹¹ mol m⁻² s⁻¹ at pH 2. These rates are 3–4 orders of magnitude slower than the oxidative dissolution of pyrite and 5 orders of magnitude slower than that of arsenopyrite. Ferric arsenate dissolution rates range from 6.14 × 10⁻⁹ mol m⁻² s⁻¹ at pH 2 to 1.66 × 10⁻⁹ mol m⁻² s⁻¹ at pH 5. Among the common As minerals, scorodite has the lowest solubility and dissolution rate. Whereas ferric arsenate is not a suitable compound for As control in mine effluents, nanocrystalline scorodite that can be easily precipitated at ambient pressure and temperature conditions would be satisfactory in meeting the regulatory guidelines at pH 3–4.  相似文献   

Regional and temporal variations in CO₂/He,He/He and δC along the North Anatolian Fault Zone,Turkey     

G.A.M. de Leeuw  D.R. Hilton  N. Güleç  H. Mutlu 《Applied Geochemistry》2010

New He and C relative abundance, isotope and concentration results from nine geothermal locations situated along an 800-km transect of the North Anatolian Fault Zone (NAFZ), Turkey, that were monitored during the period November 2001–November 2004, are reported. The geothermal waters were collected every 3–6 months to study possible links between temporal geochemical variations and seismic activity along the NAFZ. At the nine sample locations, the He isotope ratios range from 0.24 to 2.3R_A, δ¹³C values range from −4.5 to +5.8‰, and CO₂/³He ratios range from 5 × 10⁹ to 5 × 10¹⁴. The following geochemical observations are noted: (1) the highest ³He/⁴He ratios are found near the Galatean volcanic region, in the central section of the NAFZ, (2) at each of the nine sample locations, the ³He/⁴He ratios are generally constant; however, CO₂/³He ratios and He contents both show one order of magnitude variability, and δ¹³C values show up to ∼4‰ variability, and (3) at all locations (except Re?adiye), δ¹³C values show positive correlations with CO₂ contents. The results indicate that at least three processes are necessary to account for the geochemical variations: (1) binary mixing between crustal and mantle-derived volatiles can explain the general characteristics of ³He/⁴He ratios, δ¹³C values, and CO₂/³He ratios at the nine sample locations; (2) preferential degassing of He from the geothermal waters is responsible for variations in CO₂/³He values and He contents at each sample location; and (3) CO₂ dissolution followed by calcite precipitation is responsible for variations in CO₂ contents and δ¹³C values at most locations. For each of the geochemical parameters, anomalies are defined in the temporal record by values that fall outside two standard deviations of average values at each specific location. Geochemical anomalies that may be related to seismic activity are recorded on June 28, 2004 at Yalova, where a M = 4.2 earthquake occurred 43 days earlier at 15 km distance from the sample location, and on April 7, 2003 at Efteni, where a M = 4.0 earthquake occurred 44 days later at a distance of 12 km. At both locations, the sampling periods containing geochemical anomalies were preceded by an increase in M ? 3 earthquakes occurring within 60 days and less than 40 km distance.  相似文献   

Surface heat flow and CO₂ emissions within the Ohaaki hydrothermal field,Taupo Volcanic Zone,New Zealand     

Clinton Rissmann  Bruce Christenson  Cynthia Werner  Matthew Leybourne  Jim Cole  Darren Gravley 《Applied Geochemistry》2012

Carbon dioxide emissions and heat flow have been determined from the Ohaaki hydrothermal field, Taupo Volcanic Zone (TVZ), New Zealand following 20 a of production (116 MW_e). Soil CO₂ degassing was quantified with 2663 CO₂ flux measurements using the accumulation chamber method, and 2563 soil temperatures were measured and converted to equivalent heat flow (W m⁻²) using published soil temperature heat flow functions. Both CO₂ flux and heat flow were analysed statistically and then modelled using 500 sequential Gaussian simulations. Forty subsoil CO₂ gas samples were also analysed for stable C isotopes. Following 20 a of production, current CO₂ emissions equated to 111 ± 6.7 T/d. Observed heat flow was 70 ± 6.4 MW, compared with a pre-production value of 122 MW. This 52 MW reduction in surface heat flow is due to production-induced drying up of all alkali–Cl outflows (61.5 MW) and steam-heated pools (8.6 MW) within the Ohaaki West thermal area (OHW). The drying up of all alkali–Cl outflows at Ohaaki means that the soil zone is now the major natural pathway of heat release from the high-temperature reservoir. On the other hand, a net gain in thermal ground heat flow of 18 MW (from 25 MW to 43.3 ± 5 MW) at OHW is associated with permeability increases resulting from surface unit fracturing by production-induced ground subsidence. The Ohaaki East (OHE) thermal area showed no change in distribution of shallow and deep soil temperature contours despite 20 a of production, with an observed heat flow of 26.7 ± 3 MW and a CO₂ emission rate of 39 ± 3 T/d. The negligible change in the thermal status of the OHE thermal area is attributed to the low permeability of the reservoir beneath this area, which has limited production (mass extraction) and sheltered the area from the pressure decline within the main reservoir. Chemistry suggests that although alkali–Cl outflows once contributed significantly to the natural surface heat flow (∼50%) they contributed little (<1%) to pre-production CO₂ emissions due to the loss of >99% of the original CO₂ content due to depressurisation and boiling as the fluids ascended to the surface. Consequently, the soil has persisted as the major (99%) pathway of CO₂ release to the atmosphere from the high temperature reservoir at Ohaaki. The CO₂ flux and heat flow surveys indicate that despite 20 a of production the variability in location, spatial extent and magnitude of CO₂ flux remains consistent with established geochemical and geophysical models of the Ohaaki Field. At both OHW and OHE carbon isotopic analyses of soil gas indicate a two-stage fractionation process for moderate-flux (>60 g m⁻² d⁻¹) sites; boiling during fluid ascent within the underlying reservoir and isotopic enrichment as CO₂ diffuses through porous media of the soil zone. For high-flux sites (>300 g m⁻² d⁻¹), the δ¹³CO₂ signature (−7.4 ± 0.3‰ OHW and −6.5 ± 0.6‰ OHE) is unaffected by near-surface (soil zone) fractionation processes and reflects the composition of the boiled magmatic CO₂ source for each respective upflow. Flux thresholds of <30 g m⁻² d⁻¹ for purely diffusive gas transport, between 30 and 300 g m⁻² d⁻¹ for combined diffusive–advective transport, and ?300 g m⁻² d⁻¹ for purely advective gas transport at Ohaaki were assigned. δ¹³CO₂ values and cumulative probability plots of CO₂ flux data both identified a threshold of ∼15 g m⁻² d⁻¹ by which background (atmospheric and soil respired) CO₂ may be differentiated from hydrothermal CO₂.  相似文献   

Radium uptake during barite recrystallization at 23 ± 2 °C as a function of solution composition: An experimental Ba and Ra tracer study     

E. Curti  K. Fujiwara  J. Tits  A. Kitamura  W. Müller 《Geochimica et cosmochimica acta》2010,74(12):3553-5422

High-purity synthetic barite powder was added to pure water or aqueous solutions of soluble salts (BaCl₂, Na₂SO₄, NaCl and NaHCO₃) at 23 ± 2 °C and atmospheric pressure. After a short pre-equilibration time (4 h) the suspensions were spiked either with ¹³³Ba or ²²⁶Ra and reacted under constant agitation during 120-406 days. The pH values ranged from 4 to 8 and solid to liquid (S/L) ratios varied from 0.01 to 5 g/l. The uptake of the radiotracers by barite was monitored through repeated sampling of the aqueous solutions and radiometric analysis. For both ¹³³Ba and ²²⁶Ra, our data consistently showed a continuous, slow decrease of radioactivity in the aqueous phase.Mass balance calculations indicated that the removal of ¹³³Ba activity from aqueous solution cannot be explained by surface adsorption only, as it largely exceeded the 100% monolayer coverage limit. This result was a strong argument in favor of recrystallization (driven by a dissolution-precipitation mechanism) as the main uptake mechanism. Because complete isotopic equilibration between aqueous solution and barite was approached or even reached in some experiments, we concluded that during the reaction all or substantial fractions of the initial solid had been replaced by newly formed barite.The ¹³³Ba data could be successfully fitted assuming constant recrystallization rates and homogeneous distribution of the tracer into the newly formed barite. An alternative model based on partial equilibrium of ¹³³Ba with the mineral surface (without internal isotopic equilibration of the solid) could not reproduce the measured activity data, unless multistage recrystallization kinetics was assumed. Calculated recrystallization rates in the salt solutions ranged from 2.8 × 10⁻¹¹ to 1.9 × 10⁻¹⁰ mol m⁻² s⁻¹ (2.4-16 μmol m⁻² d⁻¹), with no specific trend related to solution composition. For the suspensions prepared in pure water, significantly higher rates (∼5.7 × 10⁻¹⁰ mol m⁻² s⁻¹ or ∼49 μmol m⁻² d⁻¹) were determined.Radium uptake by barite was determined by monitoring the decrease of ²²⁶Ra activity in the aqueous solution with alpha spectrometry, after filtration of the suspensions and sintering. The evaluation of the Ra uptake experiments, in conjunction with the recrystallization data, consistently indicated formation of non-ideal solid solutions, with moderately high Margules parameters (W_AB = 3720-6200 J/mol, a₀ = 1.5-2.5). These parameters are significantly larger than an estimated value from the literature (W_AB = 1240 J/mol, a₀ = 0.5).In conclusion, our results confirm that radium forms solid solutions with barite at fast kinetic rates and in complete thermodynamic equilibrium with the aqueous solutions. Moreover, this study provides quantitative thermodynamic data that can be used for the calculation of radium concentration limits in environmentally relevant systems, such as radioactive waste repositories and uranium mill tailings.  相似文献   

Chemical weathering, river geochemistry and atmospheric carbon fluxes from volcanic and ultramafic regions on Luzon Island, the Philippines     

H.H. Schopka  L.A. Derry 《Geochimica et cosmochimica acta》2011,75(4):978-7854

We investigated rates of chemical weathering of volcanic and ophiolitic rocks on Luzon Island, the Philippines. Luzon has a tropical climate and is volcanically and tectonically very active, all factors that should enhance chemical weathering. Seventy-five rivers and streams (10 draining ophiolites, 65 draining volcanic bedrock) and two volcanic hot springs were sampled and analyzed for major elements, alkalinity and ⁸⁷Sr/⁸⁶Sr. Cationic fluxes from the volcanic basins are dominated by Ca²⁺ and Mg²⁺ and dissolved silica concentrations are high (500-1900 μM). Silica concentrations in streams draining ophiolites are lower (400-900 μM), and the cationic charge is mostly Mg²⁺. The areally weighted average CO₂ export flux from our study area is 3.89 ± 0.21 × 10⁶ mol/km²/yr, or 5.99 ± 0.64 × 10⁶ mol/km²/yr from ophiolites and 3.58 ± 0.23 × 10⁶ mol/km²/yr from volcanic areas (uncertainty given as ±1 standard error, s.e.). This is ∼6-10 times higher than the current best estimate of areally averaged global CO₂ export by basalt chemical weathering and ∼2-3 times higher than the current best estimate of CO₂ export by basalt chemical weathering in the tropics. Extrapolating our findings to all tropical arcs, we estimate that around one tenth of all atmospheric carbon exported via silicate weathering to the oceans annually is processed in these environments, which amount to ∼1% of the global exorheic drainage area. Chemical weathering of volcanic terranes in the tropics appears to make a disproportionately large impact on the long-term carbon cycle.  相似文献   

Influence of waterfall aeration and seasonal temperature variation on the iron and arsenic attenuation rates in an acid mine drainage system     

Chun-Jung Chen  Wei-Teh Jiang 《Applied Geochemistry》2012

Dramatic seasonal changes in water chemistry and precipitate mineralogy associated with acid-mine drainage (AMD) in the waterfall and creek sections of the Chinkuashih area, northern Taiwan were investigated. Special attention has been paid to the kinetic effects of seasonal temperature variation and waterfall aeration. Precipitation of schwertmannite associated with removal of metals and As are indicated by delicate growth microstructures on precipitate surfaces, X-ray diffraction data, and downstream reductions of metal and As concentrations. Geochemical modeling suggested a downstream increase of the degree of saturation/supersaturation with respect to schwertmannite in the waterfall section, which can be attributed to high Fe²⁺ oxidation rates. The waterfall section was characterized by high rates and model rate constants of Fe²⁺ oxidation (6.1–6.7 × 10⁻⁶ mol L⁻¹ s⁻¹ and 2.7–2.9 × 10⁻² s⁻¹) and Fe (schwertmannite) precipitation (1.7–2.1 × 10⁻⁶ mol L⁻¹ s⁻¹ and 3.5–4.1 × 10⁻⁷ mol L⁻¹ s⁻¹). A high As sorption rate (4.7–6.3 × 10⁻⁹ mol L⁻¹ s⁻¹) and low As distribution coefficient (7.9–11.8 × 10⁻⁹ mol⁻¹ L) were observed. The creek section showed up to 1–2 orders of magnitude slower rates and lower rate constants than the waterfall section and had seasonal variations comparable to those in areas polluted by AMD elsewhere. The summer rates were 4–5 times higher than the winter rates in the creek section, and are largely attributed to a temperature effect. In contrast, the seasonal differences in rate and rate constant were small in the waterfall section. Several factors associated with the waterfall aeration in addition to elevated temperature and As concentration enhanced Fe and As attenuation in the waterfall section. The waterfall effects on Fe precipitation rate were enhanced when the flow rate was large in the winter. Despite the remarkable removal of metals and As by the rapid precipitation of As-bearing schwertmannite, large effluent loads of potentially hazardous contaminants including As, Cu and Zn discharged to the sea in the Chinkuashih area.  相似文献   

Dissolution and carbonation of a serpentinite: Inferences from acid attack and high P-T experiments performed in aqueous solutions at variable salinity     

Andrea Orlando  Daniele BorriniLuigi Marini 《Applied Geochemistry》2011,26(8):1569-1583

Dissolution experiments on a serpentinite were performed at 70 °C, 0.1 MPa, in H₂SO₄ solution, in open and closed systems, in order to evaluate the overall dissolution rate of mineral components over different times (4, 9 and 24 h). In addition, the serpentinite powder was reacted with a NaCl-bearing aqueous solution and supercritical CO₂ for 24 h at higher pressures (9-30 MPa) and temperatures (250-300 °C) either in a stirred reactor or in an externally-heated pressure vessel to assess both the dissolution rate of serpentinite minerals and the progress of the carbonation reaction. Results show that, at 0.1 MPa, MgO extraction from serpentinite ranges from 82% to 98% and dissolution rate varies from 8.5 × 10⁻¹⁰ mole m⁻² s⁻¹ to 4.2 × 10⁻⁹ mole m⁻² s⁻¹. Attempts to obtain carbonates from the Mg-rich solutions by increasing their pH failed since Mg- and NH₄- bearing sulfates promptly precipitated. On the other hand, at higher pressures, significant crystallization (5.0-10.4 wt%) of Ca- and Fe-bearing magnesite was accomplished at 30 MPa and 300 °C using 100 g L⁻¹ NaCl aqueous solutions. The corresponding amount of CO₂ sequestered by crystallization of carbonates is 9.4-15.9 mole%. Dissolution rate (from 6.3 × 10⁻¹¹ mole m⁻² s⁻¹ to 1.3 × 10⁻¹⁰ mole m⁻² s⁻¹) is lower than that obtained at 0.1 MPa and 70 °C but it is related to pH values much higher (3.3-4.4) than that (−0.65) calculated for the H₂SO₄ solution.Through a thorough review of previous experimental investigations on the dissolution kinetics of serpentine minerals the authors propose adopting: (i) the log rate [mole m⁻² s⁻¹] value of −12.08 ± 0.16 (1σ), as representative of the neutral dissolution mechanism at 25 °C and (ii) the following relationship for the acidic dissolution mechanism at 25 °C: