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   
1 [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] 下一页 » 末  页»
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1.
We investigate our ability to assess transfer of hexavalent chromium, Cr(VI), from the soil to surface runoff by considering the effect of coupling diverse adsorption models with a two‐layer solute transfer model. Our analyses are grounded on a set of two experiments associated with soils characterized by diverse particle size distributions. Our study is motivated by the observation that Cr(VI) is receiving much attention for the assessment of environmental risks due to its high solubility, mobility, and toxicological significance. Adsorption of Cr(VI) is considered to be at equilibrium in the mixing layer under our experimental conditions. Four adsorption models, that is, the Langmuir, Freundlich, Temkin, and linear models, constitute our set of alternative (competing) mathematical formulations. Experimental results reveal that the soil samples characterized by the finest grain sizes are associated with the highest release of Cr(VI) to runoff. We compare the relative abilities of the four models to interpret experimental results through maximum likelihood model calibration and four model identification criteria (i.e., the Akaike information criteria [AIC and AICC] and the Bayesian and Kashyap information criteria). Our study results enable us to rank the tested models on the basis of a set of posterior weights assigned to each of them. A classical variance‐based global sensitivity analysis is then performed to assess the relative importance of the uncertain parameters associated with each of the models considered, within subregions of the parameter space. In this context, the modelling strategy resulting from coupling the Langmuir isotherm with a two‐layer solute transfer model is then evaluated as the most skilful for the overall interpretation of both sets of experiments. Our results document that (a) the depth of the mixing layer is the most influential factor for all models tested, with the exception of the Freundlich isotherm, and (b) the total sensitivity of the adsorption parameters varies in time, with a trend to increase as time progresses for all of the models. These results suggest that adsorption has a significant effect on the uncertainty associated with the release of Cr(VI) from the soil to the surface runoff component.  相似文献   
2.
The distribution of dissolved and participate concentrations of As, Cr and V was investigated in the mixing area of the Po river in five surveys over the period March 1992-March 1995. The data obtained indicate noticeable contamination of coastal waters of the northern Adriatic with Cr but not As or V. Total dissolved concentrations for As and V were comparable with oceanic levels but were higher by a factor of 4 for Cr. These results suggest either low anthropogenic inputs of As and V, from terrigenous and atmospheric sources, or efficient removal mechanisms. The investigated metals had low reactivity during freshwater-seawater mixing and the distribution of concentrations in the dissolved and solid phases suggests that the dilution process is the main factor controlling the transport of these metals to the sea in low-to-medium solid transport conditions. Further investigations are required to elucidate the behavior of these metals during high solid transport conditions. Significant changes in the speciation of As occurred during the transition between the two end-member matrices. In the coastal waters of the northern Adriatic, the arsenite fraction in winter, and the arsenite and dimethylarsinate fractions in summer increased with respect to riverine waters. Changes in the speciation of chromium were minor, but also showed a small increase in reduced species in marine waters.  相似文献   
3.
地下连续墙治理地下水污染   总被引:12,自引:1,他引:11  
介绍一种治理已被严重污染的地下水的方法。即修建一道底部深入到不透水岩层的地下墙,把污染物封闭在由底部不透水岩层和周围地下防渗墙组成的“地下盆”中,降低周围地下水中有害物质的浓度,然后再治理封闭圈内的污染物,以达到彻底根治地下水污染的目的。  相似文献   
4.
 We have investigated a well-ordered sample of natural Cr-bearing dickite from Nowa Ruda (Lower Silesia, Poland) using electron paramagnetic resonance (EPR) at X- and Q-band frequencies (9.42 and 33.97 GHz, respectively) and optical diffuse reflectance spectroscopy. The observation of the spin-forbidden transitions at 15500 and 14690 cm−1 allows us to unambiguously identify the major contribution of octahedrally coordinated Cr3+ ions in the optical spectrum. The X- and Q-band EPR spectra show two superposed Cr3+ signals. The corresponding fine-structure parameters were determined at room temperature and 145 K. These results suggest the substitution of Cr3+ for Al3+ in equal proportions in the two unequivalent octahedral sites of the dickite structure. In kaolin group minerals, the distortion around Cr3+ ions (λ≈ 0.2–0.4) in Al sites is significantly less rhombic than that observed around Fe3+ ions (λ≈ 0.6–0.8). Received: 29 June 2001 / Accepted: 22 October 2001  相似文献   
5.
Stephan Klemme   《Lithos》2004,77(1-4):639-646
The position of the transition from spinel peridotite to garnet peridotite in a simplified chemical composition has been determined experimentally at high pressures and high temperatures. The univariant reaction MgCr2O4+2Mg2Si2O6=Mg3Cr2Si3O12+Mg2SiO4, has a negative slope in PT space between 1200 °C and 1600 °C. The experimental results, combined with assessed thermodynamic data for MgCr2O4, MgSiO3 and Mg2SiO4 give the entropy and enthalpy of formation of knorringite garnet (Mg3Cr2Si3O12). Thermodynamic calculations in simplified chemical compositions indicate that Cr shifts the garnet-in reaction to much higher pressures than previously anticipated. Moreover, in Cr-bearing systems a pressure–temperature field exists where garnet and spinel coexist. The width of this divariant field strongly depends on the Cr/(Cr+Al) of the system.  相似文献   
6.
In the Saoura, the brachiopod shell beds, so-called niveau coralligène, correspond to a major shell deposit dated to the Late Emsian. Brachiopods and crinoids dominate the benthic assemblage that contains also corals, bryozoans, trilobites, goniatites, and orthocones. This major level has a large geographic distribution and it is characterized by a wide brachiopod diversity due to time-averaging, taphonomic feedback and alternate bottom conditions changing from soft to shelly and firm. This kind of brachiopod association is linked to a transgressive onlap system. At regional extent, we can correlate this major shell bed to similar shell deposits from the Ahnet-Mouydir, Tindouf, and Zemmour areas. It indicates an important transgressive event underlined by change in the sedimentation from detritic deposits to carbonate sediments. To cite this article: A. Ouali Mehadji et al., C. R. Geoscience 336 (2004).  相似文献   
7.
The Bulqiza ultramafic massif, which is part of the eastern Mirdita ophiolite of northern Albania, is world renowned for its high-Cr chromitite deposits. High-Cr chromitites hosted in the mantle section are the crystallized products of boninitic melts in a supra-subduction zone (SSZ). However, economically important high-Al chromitites are also present in massive dunite of the mantle-crust transition zone (MTZ). Chromian-spinel in the high-Al chromitites and dunites of the MTZ have much lower Cr# values (100Cr/(Cr+Al)) (47.7–55.1 and 46.5–51.7, respectively) than those in the high-Cr chromitites (78.2–80.4), harzburgites (72.6–77.9) and mantle dunites (79.4–84.3). The chemical differences in these two types of chromitites are reflected in the behaviors of their platinum-group elements (PGE). The high-Cr chromitites are rich in IPGE relative to PPGE with 0.10–0.45 PPGE/IPGE ratios, whereas the high-Al chromitites have relatively higher PPGE/IPGE ratios between 1.20 and 7.80. The calculated melts in equilibrium with the high-Cr chromitites are boninitic-like, and those associated with the high-Al chromitites are MORB-like but with hydrous, oxidized and TiO2-poor features. We propose that the coexistence of both types of chromitites in the Bulqiza ultramafic massif may indicates a change in magma composition from MORB-like to boninitic-like in a proto-forearc setting during subduction initiation.  相似文献   
8.
为了解决微米铁的重力沉降问题,提高微米铁修复地下水Cr(Ⅵ)污染的原位修复效果,本文利用黄原胶对微米铁进行改性,并通过沉降实验探究改性微米铁浆液的稳定性,同时选择Cr(Ⅵ)作为目标污染物,探究黄原胶改性微米铁去除地下水Cr(Ⅵ)污染的降解能力。实验结果显示:当黄原胶的投加质量浓度分别为0.0、1.0、1.5、2.0、2.5、3.0、6.0 g/L时,改性微米铁浆液的悬浮稳定性逐渐得到加强,在5 h沉降实验结束时,对应的相对分光光度值分别为0.05、0.25、0.46、0.57、0.65、0.73和0.87;黄原胶具有抑制微米铁吸附Cr(Ⅵ)的能力,其可促进Cr(Ⅵ)的还原,提高Cr(Ⅵ)的去除率;随着黄原胶投加质量浓度的增加,对应的Cr(Ⅵ)去除率分别为33.4%、41.2%、47.4%、51.1%、53.0%、63.9%和64.1%;6.0 g/L黄原胶改性的微米铁浆液具有最佳的悬浮稳定性,黄原胶的投加提高了微米铁的反应活性,但当黄原胶投加质量浓度超过3.0 g/L时,其对Cr(Ⅵ)的去除率没有显著提高;黄原胶投加质量浓度越大,黄原胶的缓冲作用就越明显。  相似文献   
9.
渗透反应格栅(permeable reactive barrier,PRB)在国外被广泛应用于场地尺度的地下水污染修复,因其无须外源动力、不占地面空间、运行成本低等优势在国内受到广泛关注。不同场地水文地质条件、污染物类型、污染羽分布具有差异性,前期场地调查、反应材料的筛选、反应墙尺寸结构的设计对于PRB的有效运行至关重要。本文以PRB修复河南某Cr(Ⅵ)污染场地为例,详细阐述场地调查、材料筛选、材料反应参数确定、PRB结构优化等方面的研究过程及成果,可为后续PRB修复技术的应用提供参考。研究结果表明:PRB修复技术适用于该场地,铸铁与活性炭混合材料为最佳修复材料;反应门长40 m(反应材料厚2 m,上下游分别为2 m厚砾石层),东西两侧隔水墙长为60 m的U型漏斗-门系统型PRB,可有效捕获并修复污染羽,工程成本远低于连续反应墙式PRB,为该场地修复最优PRB结构类型。  相似文献   
10.
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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