where k (M− 2 s− 1) can be determined from the
in the pH range 2 to 5, from 5 to 40 °C and 0.01 to 1 M.The effect of pH and ionic strength on the reaction suggest that the rates are due to
where H2A = H2CrO4, HA = HCrO4, H2B = H2SO3 and HB = HSO3. The overall rate expression over the investigated pH range can be determined from
k=kH2A–H2B(αH2A)(αH2B)2+kHA–H2B(αHA)(αH2B)2+kH2A–HB(αH2A)(αHB)2
with kH2A−H2B = 5.0 × 107, kHA–H2B = 1.5 × 106 and kH2A–HB = 6.7 × 107.Fe(III) in the range 1.5 to 20 μM exerts a small catalytic effect on the reaction and significantly lowers the initial concentration of Cr(VI) compared to the nominal value. Contrary to Fe(III), formaldehyde (20 to 200 μM) reacts with S(IV) to form the hydroxymethanesulfonate adduct (CH2OHSO3), which does not react with Cr(VI). Major cations Mg2+ and some minor elements such as Ba2+ and Cu2+ did not affect the rates. The application of this rate law to environmental conditions suggest that this reaction may have a role in acidic solutions (aerosols and fog droplets). This reaction becomes more important in the presence of high Fe(III) and low HMS concentrations, contributing to affect the atmospheric transport of chromium species and the distribution of redox species of chromium, which reach surface water from atmospheric depositions.  相似文献   
48.
A global heat and freshwater forcing dataset for ocean models     
Frank Rske 《Ocean Modelling》2006,11(3-4):235-297
A global dataset based on the ECMWF Re-Analyses (ERA) is presented that can be used as surface boundary conditions for ocean models with sea-ice components. The definition of these conditions is based on bulk formulae. To study the mean ocean circulation, a mean annual cycle on a daily basis was constructed from ERA for all relevant parameters including wind stress. Continental runoff is considered by using information about the catchment areas of the rivers and about the main drainage basins. The bulk formulae were extended by using sea ice concentration.To estimate meridional heat transports (MHT) and to avoid any drift in ocean model simulations, the heat and fresh water budgets have been closed by applying an inverse procedure to fine-tune the fluxes towards observed transports. To improve the MHTs on the Southern Hemisphere the winds and the short wave radiation at southern higher latitudes should be corrected. Furthermore, tests were performed concerning short wave radiation which was increased in the tropics and decreased in the subsidence zones.The heat and fresh water fluxes are assessed by using a scheme of Macdonald and Wunsch based on hydrographic sections. The net heat fluxes of ERA and of the forcing dataset are consistent with the heat flux divergences and convergences estimated by this scheme except for parts of the South Atlantic and the Indian Ocean sector of the Southern Ocean where none of these datasets is consistent with these estimates. In the subtropical South Indian Ocean the forcing dataset is consistent with these estimates while ERA are not. The flux components of ERA and the forcing dataset were compared to several observational datasets (SRB, SOC, HOAPS, GPCP, and CMAP). For each component, at least one of these datasets (especially HOAPS) supports the effects of the inverse procedure and the bulk formulae almost globally with some regional exceptions: short wave radiation in the tropical oceans and the subtropical North Atlantic, latent heat flux at higher latitudes, and precipitation in the northern North Atlantic.Comparisons to the NCAR/NCEP Re-Analyses (NRA) (versions 1 and 2) and the ECHAM model in place of ERA lead to similar results. In the North Atlantic the net heat fluxes of the model based datasets approach the hydrographic estimate with increasing resolution. Applied to any ocean/sea-ice model and compared to ERA, the forcing dataset would induce only a relative small net sea-surface buoyancy loss.A comparison of the forcing dataset to measurements made using one buoy deployed in the western Pacific warm pool and five buoys deployed in the subduction region of the Northeast Atlantic shows that at the site of the first buoy the net heat fluxes of the forcing dataset are in poorer agreement than those of ERA. At the sites of two subduction buoys both datasets show the same level of agreement within the error bars specified. At the sites of the three remaining subduction buoys the forcing dataset shows a marginal improvement on ERA.  相似文献   
49.
Recovery of thermohaline circulation under CO2 stabilization and overshoot scenarios   总被引:1,自引:0,他引:1  
Norikazu. Nakashiki  Dong-Hoon Kim  Frank O. Bryan  Yoshikatsu Yoshida  Daisuke Tsumune  Koki Maruyama  Hideyuki Kitabata 《Ocean Modelling》2006,15(3-4):200
In this study we examine the behavior of the thermohaline circulation, as simulated by the Community Climate System Model version 3 (CCSM3), for several centuries following CO2 stabilization for the SRES B1 and A1B scenarios and for an “overshoot” scenario in which CO2 levels temporarily reach the same level as in the A1B scenario before declining to an ultimate stabilization level that is identical to the B1 case. While we find no evidence for irreversible changes of the thermohaline circulation in the overshoot experiment, the interplay of the different timescales of the temperature response of the surface and interior ocean does lead to a number of differences in the long-term response of the ocean between it and the B1 stabilization scenario where the same GHG levels are approached by different paths. The stronger initial warming and its slow penetration into the deeper ocean, followed by a transient surface cooling in the overshoot scenario leads to lower static stability, deeper mixing, and a more rapid recovery of the thermohaline circulation than in the B1 stabilization scenario. While the overshoot scenario recovers surface conditions (e.g. SST, sea ice extent) very similar to the B1 scenario shortly after reaching the same GHG levels, the additional accumulation of heat in the interior ocean during the period of higher forcing causes the global mean ocean temperature and steric sea level to remain higher than in the B1 stabilization scenario for at least another several centuries.  相似文献   
50.
Regional-scale hydrothermal alteration in the Central Blake River Group,western Abitibi subprovince,Canada: implications for VMS prospectivity   总被引:1,自引:0,他引:1  
Mark?D.?HanningtonEmail author  Frank?Santaguida  Ingrid?M.?Kjarsgaard  Larry?M.?Cathles 《Mineralium Deposita》2003,38(4):393-422
The Late Archean Blake River Group is a thick succession of predominantly mafic volcanic rocks within the southern zone of the Abitibi greenstone belt. It contains a number of silicic volcanic centers of different size, including the large Noranda volcanic complex, which is host to 17 past-producing volcanogenic massive sulfide deposits. The Noranda complex consists of a 7- to 9-km-thick succession of bimodal mafic and felsic volcanic rocks erupted during five major cycles of volcanism. Massive sulfide formation coincided with a period of intense magmatic activity (cycle III) and the formation of the Noranda cauldron. Hydrothermal alteration in these rocks is interpreted to reflect large-scale hydrothermal fluid flow associated with rapid crustal extension and rifting of the volcanic complex. The alteration includes abundant albite, chlorite, epidote and quartz (silicification), which exhibit broad stratigraphic and structural control and correlate with previously mapped whole-rock oxygen isotope zonation. The Mine Sequence volcanic rocks are characterized by abundant iron-rich chlorite (Fe/Fe+Mg >0.5), hydrothermal amphibole (ferroactinolite) and coarse-grained epidote of clinozoisite composition (<10 wt% Fe 2O 3). Volcanic rocks of the pre-cauldron sequences, which contain only subeconomic stringer mineralization, are characterized by less abundant chlorite and mainly fine-grained epidote (>10 wt% Fe 2O 3) lacking the clinozoisite solid solution. Alteration in the Mine Sequence volcanic rocks persists along strike well beyond the limits of the main ore deposits (as far as several tens of kilometers) and can be readily distinguished from greenschist facies metamorphic assemblages at a regional scale. The lack of similar alteration in the pre-cauldron sequences is consistent with limited 18O-depletion and suggests that the early history of the volcanic complex did not support large-scale, high-temperature fluid flow in these rocks. Comparisons with a much smaller, barren volcanic complex in nearby Ben Nevis township reveal important differences in the alteration mineralogy between volcanoes of different size, with implications for area selection during regional-scale mineral exploration. The Ben Nevis Complex consists of a 3- to 4-km-thick succession of mafic, intermediate and felsic volcanic rocks centered on a small subvolcanic intrusion. Alteration of the volcanic rocks comprises mainly low-temperature assemblages of prehnite, pumpellyite, magnesium-rich chlorite (Fe/Fe+Mg <0.5), iron-rich epidote (>10 wt% Fe 2O 3) and calcite. Actinolite ± magnetite alteration occurs proximal to the intrusive core of the complex, but the limited extent of this alteration indicates only local high-temperature fluid circulation adjacent to the intrusion. A distal zone of carbonate alteration is located 4–6 km from the center of the volcano. Although iron-bearing carbonates are present locally within this zone, the absence of siderite argues against a high-temperature origin for this alteration. These observations do not offer positive encouragement for the existence of a fossil geothermal system of sufficient size or intensity to have produced a large massive sulfide deposit.  相似文献   
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41.
The pK1* and pK2* for the dissociation of carbonic acid in seawater have been determined from 0 to 45°C and S = 5 to 45. The values of pK1* have been determined from emf measurements for the cell:
Pt](1 − X)H2 + XCO2|NaHCO3, CO2 in synthetic seawater|AgC1; Ag
where X is the mole fraction of CO2 in the gas. The values of pK2* have been determined from emf measurements on the cell:
Pt, H2(g, 1 atm)|Na2CO3, NaHCO3 in synthethic seawater|AgC1; Ag
The results have been fitted to the equations:
lnK*1 = 2.83655 − 2307.1266/T − 1.5529413 lnT + (−0.20760841 − 4.0484/T)S0.5 + 0.08468345S − 0.00654208S1
InK*2 = −9.226508 − 3351.6106/T− 0.2005743 lnT + (−0.106901773 − 23.9722/T)S0.5 + 0.1130822S − 0.00846934S1.5
where T is the temperature in K, S is the salinity, and the standard deviations of the fits are σ = 0.0048 in lnK1* and σ = 0.0070 in lnK2*.Our new results are in good agreement at S = 35 (±0.002 in pK1*and ±0.005 in pK2*) from 0 to 45°C with the earlier results of Goyet and Poisson (1989). Since our measurements are more precise than the earlier measurements due to the use of the Pt, H2|AgCl, Ag electrode system, we feel that our equations should be used to calculate the components of the carbonate system in seawater.  相似文献   
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Euglena gracilis makes two small Cd-binding proteins/peptides (Cd-BP I and Cd-BP II) in response to exposure to Cd2+. These proteins migrate slower than mammalian Cd-metallothionein (Cd-Mt) through Sephadex G-75, but like Cd-Mt also contain Zn and are separated into two species when chromatographed over a DEAE column. Both BPs are much less stable than Cd-Mt under acidic conditions. One source of this instability is that at least Cd-BP II contains acid-labile sulfide co-ordinated to the metals. It has been quantitated in Cd-BP II and shown to have a value of 1·25 ± 0·10 S2−/Cd. The reactivity of the Cd-binding sites in ligand substitution and thioldisulfide exchange reactions has been assessed. The reactions of Cd-BP I and II with pyridylazoresorcinol (PAR) were slow and displayed complex kinetic behavior. Similarly, both Cd-BPs react slowly and with complicated kinetics with 5,5′-dithiobis-(2-nitrobenzoate).  相似文献   
45.
Vietnam is in the process of introducing adaptive management based on indicators and time-series to manage its marine fisheries. The development of indicator-based frameworks for fisheries management has accelerated in recent years. This article describes the suite of indicators being suggested or used in Vietnam including the data-collection system. The Vietnamese approach is supported by an institutional structure consisting of a multi-disciplinary advisory system to facilitate the process of using indicators and to introduce knowledge-based management. The article concludes by identifying current problems and weaknesses and by providing suggestions for future improvement of the system.  相似文献   
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The rates of the reduction of Cr(VI) with S(IV) were measured in deaerated NaCl solution as a function of pH, temperature and ionic strength. The rates of the reaction were found to be first order with respect to Cr(VI) and second order with respect to S(IV), in agreement with previous results obtained at concentrations two order higher than the present study. The reaction also showed a first-order dependence of the rates on the concentration of the proton and a small influence of temperature with an apparent energy of activation ΔHapp of 22.8 ± 3.4 kJ/mol. The rates were independent of ionic strength from 0.01 to 1 M. The rate of Cr(VI) reduction is described by the general expression
−d[Cr(VI)]/dt=k[Cr(VI)][S(IV)]2
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