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1.
Chromium is a redox-dynamic element that has many industrial uses. As a consequence, it is often introduced at elevated levels into the surface environment through human activity. Additionally, ultramafic rocks such as serpentinite are commonly enriched in chromium, and thus can also lead to appreciable levels of this element within soils and waters. In the trivalent state, it poses little hazard to biological activity, but, unfortunately, in the hexavalent state it is very toxic to living matter. One must therefore assess the oxidation state of Cr in a given system and determine the potential for transformation between valence states. The objective of this paper to is review and provide new insight on reduction reactions of Cr(VI) within natural environments. A number of aerobic and anaerobic bacteria demonstrate the enzymatic ability to reduce Cr(VI) to Cr(III); two species can even grow using Cr(VI) as the terminal electron acceptor in respiration. The ability to reduce chromium in itself is not evidence that the process will take place at appreciable levels in natural environments, however. Reduced materials such as ferrous iron or hydrogen sulfide may compete with biological pathways in the reduction of Cr(VI). On the basis of measured reaction rates and derived rate expressions, we demonstrate that biological pathways are not likely to contribute to the reduction of chromate in anaerobic systems. Ferrous iron will dominate the reduction of chromate at pH values greater than ~ 5.5, whereas hydrogen sulfide will dominate at pH values below this value. In contrast, bacteria may be the principal means by which Cr(VI) is converted to Cr(III) in aerobic environments. Thus, the process by which Cr(VI) is reduced will depend primarily on the aeration status of the system, and secondarily on pH and the concentrations of specific reduced phases.  相似文献   

2.
The oxidation states of chromium in GSJ JSO-2 (artificially contaminated soil) and three other geochemical reference materials (GSJ JSO-1, JLS-1 and JMS-1) were observed using X-ray near edge structure (XANES). For comparison, other artificially contaminated soil materials (mimic-JSO-2) were prepared by adding Cr(VI) into JSO-1. Their oxidation states of chromium were determined using XANES. The chromium contents were 1118 μg g-1 for JSO-2, 1352 μg g-1 for mimic-JSO-2 and 69-113 μg g-1 for the other reference materials. Most chromium was present as hexavalent in mimic-JSO-2. No hexavalent species were detected in other samples. These results for chromium oxidation state in JSO-2 and mimic-JSO-2 obtained with XANES resembled those obtained from a chemical extraction method. The present JSO-2 has no trace of Cr(VI), although Cr(VI) was added as a major species during preparation. On the other hand, the content of Cr(VI) obtained in mimic-JSO-2 agreed with the original Cr(VI) content. A time-elapse study showed that Cr(VI) contents in mimic-JSO-2 decreased gradually to 70% of the original abundance during 240-day preservation in dry conditions. Moreover, the abundance of Cr(VI) decreased markedly to 15% after 240 days in the wet mimic-JSO-2 containing 20% m/m of water. These experiments suggested that soil humidity enhanced the reduction of Cr(VI) and that Cr(VI) was reduced even in dry conditions. Consequently, it is reasonable to infer that Cr(VI) doped into JSO-2 was completely reduced to Cr(III) during the preservation period of 5 years. The certification of the long-term stability of the chemical form in reference materials will be much more important in future.  相似文献   

3.
铬(Cr)属于氧化还原敏感元素,在岩浆过程中是一种中度相容和轻度亲铁元素。Cr在硅酸盐地球中主要有三种价态:Cr2+、Cr3+和Cr6+。Cr存在于不同来源的矿物和岩石中,其氧化还原状态和同位素组成可以为其成因、氧化还原条件和相关成矿历史提供有价值的信息。近年来,铬同位素越来越多地应用到现代环境、古环境、行星的演化以及高温地质过程等领域中,而高温地质过程中储库的铬同位素及其分馏机理研究是其他工作的基础。尤其是随着质谱技术的发展,Cr同位素在高温环境中的分馏机制及行为也引起了更多的关注。本文主要介绍不同储库的Cr同位素组成及高温岩浆过程中Cr同位素研究的最新进展。  相似文献   

4.
We have used synchrotron-based soft X-ray core-level photoemission and adsorption spectroscopies to study the reaction of aqueous sodium chromate solutions with freshly fractured pyrite surfaces. Pyrite surfaces were reacted with 50 μM sodium chromate solution at pH 7 for reaction times between 1 min and 37 hr. Additional experiments were performed at pH 2 and pH 4 with 50 μM sodium chromate solutions and at pH 7 with 5 mM solutions. At chromate concentrations of 50 μM, all chromium present on the pyrite surface was in the form of Cr(III), while at 5 mM, both Cr(III) and Cr(VI) were present at the pyrite surface. Minor quantities of oxidized sulfur species (sulfate, sulfite, and zero-valent sulfur) were identified as reaction products on the pyrite surface. The amount of oxidized sulfur species observed on the surface was greater when pyrite was reacted with 5 mM Cr(VI) solutions because the rate of chromium deposition exceeded the rate of dissolution of pyrite oxidation products, effectively trapping Cr(VI) and oxidized sulfur species in an overlayer of iron(III)-containing Cr(III)-hydroxide. This work shows that pyrite, an extremely cheap and readily available waste material, may be suitable for the removal of hexavalent chromium from acidic to circumneutral waste streams. The reduced chromium ultimately forms a coating on the pyrite surface, which passivates the pyrite surface towards further oxidation.  相似文献   

5.
张亭亭  李江山  王平  薛强 《岩土力学》2019,40(10):3928-3936
采用硫酸亚铁(FeSO4)对铬污染土进行稳定化处理。选用浸出试验、Cr(VI)残留值试验和形态提取试验,研究了粒径和有机质对铬污染土稳定特性的影响规律。试验结果表明,粒径和有机质对铬污染土稳定特性有较大影响。粒径的减小可显著降低稳定土中Cr(VI)和总Cr的浸出浓度及稳定土中Cr(VI)的含量;当污染土粒径小于2 mm时,Fe(II)/Cr(VI)摩尔比为3,稳定土中Cr(VI)和总Cr的浸出浓度分别为4.68、8.9 mg/L,均低于我国《危险废弃物鉴别标准 浸出毒性鉴别》(GB/T5085.3-2007)的限值。有机质添加量的增加可明显降低稳定土中Cr(VI)和总Cr的浸出浓度及Cr(VI)的含量。当Fe(II)/Cr(VI)摩尔比为3时,有机质的添加量为5%,稳定土中Cr(VI)的含量为28.3 mg/kg,低于我国《土壤环境质量标准》(GB15618-2008)中工业和商业用地限值(30 mg/kg);当有机质的添加量为10%时,稳定土中Cr(VI)的含量为4.8 mg/kg,低于居住用地限值(5 mg/kg)。形态提取试验结果表明:粒径的减小可降低弱酸提取态的铬含量,增加可还原态的铬含量,而对可氧化态和残渣态的铬含量影响不大;有机质可促使弱酸提取态、可还原态的铬转化为可氧化态的铬,而残渣态的铬变化不大。稳定土中铬从活性态向较稳定态转化,是铬稳定土稳定特性和环境风险变化的根本原因。  相似文献   

6.
张亭亭  李江山  薛强  王平  熊欢  梁仕华 《岩土力学》2019,40(12):4652-4658
采用硫酸亚铁(FeSO4)对Cr(VI)污染土进行稳定化处理。研究了Fe(II)/Cr(VI)摩尔比和养护龄期对污染土稳定过程中的铬赋存形态及浸出特性的影响规律。结果表明:随着Fe(II)/Cr(VI)摩尔比和养护龄期的增加,Cr(VI)和总Cr的浸出浓度降低,稳定土中Cr(VI)的含量降低,当摩尔比为3时,Cr(VI)和总Cr的浸出浓度均低于我国《危险废弃物鉴别标准 浸出毒性鉴别》(GB/T50853―2007)的限值;当摩尔比为10时,稳定土中Cr(VI)的含量低于我国《土壤环境质量标准》(GB15618―2008)中工业和商业用地的限值(30 mg/kg);当摩尔比为20时,低于居住用地限值(5 mg/kg)。形态提取试验结果表明:FeSO4改变稳定土中铬的赋存形态,可促使铬从弱酸态向可还原态和可氧化态转化,而对残渣态的铬影响不大。Cr(VI)的浸出浓度与稳定土中的Cr(VI)含量均存在指数函数关系,且浸出试验不能全面、客观地评价铬污染土稳定效果。  相似文献   

7.
Abstract Chromian omphacite which contains up to 4 wt % Cr2O3 has been identified from low-grade metamorphic rocks in Nishisonogi, Kyushu, Japan. It occurs as aggregates, forming a thin horizon ([20 mm thick) in alayered metagabbro within a serpentinite melange zone, together with Cr-free omphacite, actino-lite, epidote and sphene. It may have been formed by the metasomatic introduction of Cr into the metagabbro from the serpentinite rather than by reaction with chromite. The structural formula, based on EPMA analyses, and the optical absorption spectrum of the chromian omphacite show that the Cr is positioned in the octahedral site.  相似文献   

8.
The photoreduction efficiency of toxic hexavalent chromium into non-toxic trivalent chromium was studied using local low-cost material and modern technology. The materials involved different iron–titanium oxide nanopowders synthesized via simple hydrothermal–hydrolysis process. X-ray diffraction and high-resolution transmission electron microscope were employed to study the structural properties of the as-prepared samples. The effects of molar ratio (Fe/Ti) and hydrothermal temperature on spectroscopic properties have been investigated using Fourier transform infrared FT-IR spectroscopy. The photocatalytic performance of hexavalent chromium was systematically studied at various conditions including initial concentration of Cr(VI), hydrothermal temperature and Fe/Ti ratios of mixed iron–titanium oxide powders. It has been found that the highest photoreduction efficiencies of Cr(VI) were 95.7 and 86.2% at initial concentrations 10 and 60 ppm of Cr(VI), respectively. The synthesized mixed Fe2O3–TiO2 photocatalyst exhibited higher efficiency of about 88% under visible light irradiation. The as-prepared mixed oxide catalyst exhibited high photocatalytic conversion efficiency and recycling stability in comparison with different commercial catalysts.  相似文献   

9.
In recent years, routine application of the stable isotope determination of chromium (Cr) in environmental and health protection research has led to the search for simpler chromite decomposition techniques. As the range of Cr isotope abundance ratios in nature is very narrow, conventional chromite decomposition techniques are no longer suitable, due to the relatively high risk of contamination during laboratory procedures. We have developed a protocol for the decomposition of chromites based on oxidation by bromic acid at room temperature. The procedure takes 15 d and requires two doses of bromic acid during the reaction period (day 1 and 8), due to the limited stability of the reagent. Chromium extracted by alkaline oxidative fusion and by bromic acid decomposition yielded statistically indistinguishable δ53Cr values, measured by multi‐collector inductively coupled plasma‐mass spectrometry following addition of a 50Cr‐54Cr double‐spike.  相似文献   

10.
A soil geochemical survey was conducted in a 27,000-km2 study area of northern California that includes the Sierra Nevada Mountains, the Sacramento Valley, and the northern Coast Range. The results show that soil geochemistry in the Sacramento Valley is controlled primarily by the transport and weathering of parent material from the Coast Range to the west and the Sierra Nevada to the east. Chemically and mineralogically distinctive ultramafic (UM) rocks (e.g. serpentinite) outcrop extensively in the Coast Range and Sierra Nevada. These rocks and the soils derived from them have elevated concentrations of Cr and Ni. Surface soil samples derived from UM rocks of the Sierra Nevada and Coast Range contain 1700–10,000 mg/kg Cr and 1300–3900 mg/kg Ni. Valley soils west of the Sacramento River contain 80–1420 mg/kg Cr and 65–224 mg/kg Ni, reflecting significant contributions from UM sources in the Coast Range. Valley soils on the east side contain 30–370 mg/kg Cr and 16–110 mg/kg Ni. Lower Cr and Ni concentrations on the east side of the valley are the result of greater dilution by granitic sources of the Sierra Nevada.Chromium occurs naturally in the Cr(III) and Cr(VI) oxidation states. Trivalent Cr is a non-toxic micronutrient, but Cr(VI) is a highly soluble toxin and carcinogen. X-ray diffraction and scanning electron microscopy of soils with an UM parent show Cr primarily occurs within chromite and other mixed-composition spinels (Al, Mg, Fe, Cr). Chromite contains Cr(III) and is highly refractory with respect to weathering. Comparison of a 4-acid digestion (HNO3, HCl, HF, HClO4), which only partially dissolves chromite, and total digestion by lithium metaborate (LiBO3) fusion, indicates a lower proportion of chromite-bound Cr in valley soils relative to UM source soils. Groundwater on the west side of the Sacramento Valley has particularly high concentrations of dissolved Cr ranging up to 50 μg L−1 and averaging 16.4 μg L−1. This suggests redistribution of Cr during weathering and oxidation of Cr(III)-bearing minerals. It is concluded that regional-scale transport and weathering of ultramafic-derived constituents have resulted in enrichment of Cr and Ni in the Sacramento Valley and a partial change in the residence of Cr.  相似文献   

11.
Chromite is a mineral with low solubility and is thus resistant to dissolution. The exception is when manganese oxides are available, since they are the only known naturally occurring oxidants for chromite. In the presence of Mn(IV) oxides, Cr(III) will oxidise to Cr(VI), which is more soluble than Cr(III), and thus easier to be removed. Here we report of chromite phenocrysts that are replaced by rhodochrosite (Mn(II) carbonate) in subseafloor basalts from the Koko Seamount, Pacific Ocean, that were drilled and collected during the Ocean Drilling Program (ODP) Leg 197. The mineral succession chromite-rhodochrosite-saponite in the phenocrysts is interpreted as the result of chromite oxidation by manganese oxides. Putative fossilized microorganisms are abundant in the rhodochrosite and we suggest that the oxidation of chromite has been mediated by microbial activity. It has previously been shown in soils and in laboratory experiments that chromium oxidation is indirectly mediated by microbial formation of manganese oxides. Here we suggest a similar process in subseafloor basalts.  相似文献   

12.
The effective influence of industry or ultramafic rocks by natural processes to soil, plants and groundwater contamination by chromium, which is often a subject of debate, was investigated for the case of the Assopos basin, Greece. The Neogene Assopos basin, is mainly composed by Tertiary and Quaternary sediments of more than 400 m thick and is characterized by brittle type deformation (fault zones, faults). Chromium in soil, ranging from 67 to 204 ppm, is mostly hosted in chromite, Fe-chromite, Cr-bearing goethite and silicates.Special attention was given to the plants, which are a major source of organic matter that serves as the driving force for Cr(VI) reduction. The increase of the Fe, Mn and Ni contents, with the increasing Cr content in the plant-roots, in particular at the external parts of roots and those of bulb-type plants, suggest reduction and immobilization of Cr(VI) and that redox reactions play a significant role to the translocation processes from root to shoot.Groundwater samples from the Assopos aquifer showed a wide spatial variability, ranging from <2 to 180 ppb Crtotal content [almost same to the Cr(VI)-values] despite their spatial association. The presence of Cr(VI)-contaminated groundwater at depths >200 m is attributed to a direct injection of Cr(VI)-rich industrial wastes at depth rather than that Cr(VI) is derived from the Assopos river or by the interaction between water and Cr-bearing rocks. The heterogeneous distribution of Cr in groundwater may be related with the intense neotectonic deformation, as is exemplified by several sharp tectonic contacts between sediment types, while the Cr content in soil is mostly depend on the transported chromite grains.  相似文献   

13.
In present work, fabrication of functionally tailored nanobiomaterials paraben-modified nanocellulose (PNC) and (2,3-epoxypropyl) trimethylammonium chloride-modified nanocellulose (EPTMAC-NC) for the remediation of trivalent and hexavalent chromium, respectively, from water streams has been done. The resulting PNC and EPTMAC-NC were characterized before and after sorption of chromium using spectroscopic and microscopic techniques. The sorption performance of PNC (23.92 mg/g; 95.67 %) and EPTMAC-NC (23.99 mg/g; 95.94 %) was evaluated for trivalent and hexavalent chromium, respectively, at 0.5 g biosorbent dose; 500 mL sample volume; 25 mg/L chromium conc.; 40 min kinetic time; pH (6.5 for trivalent and 2.5 for hexavalent chromium) and 298 K temperature. From isothermic, kinetic and thermodynamic modeling, the sorption of trivalent and hexavalent chromium was physisorption, spontaneous, feasible and endothermic in nature. These findings expose new path in the line of high performance, scalable and economic nanobiomaterials for the abatement of toxic metals from water streams.  相似文献   

14.
Soil samples from chromite mining site and its adjacent overburden dumps and fallow land of Sukinda, Odisha, were analysed for their physico-chemical, microbial and metal contents. Chromite mine soils were heterogenous mixture of clay, mud, minerals and rocks. The pH of the soils ranges between 5.87 and 7.36. The nutrient contents of the mine soils (N, P, K and organic C) were found to be extremely low. Analysis of chromite mine soils revealed accumulation of a number of metals in high concentrations (Fe > Cr > Mn > Ni > Zn > Pb > Sr) which exceeded ecotoxicological limits in soil. Correlation and cluster analysis of metals revealed a strong relation between Cr, Ni, Fe, Mn among the different attributes studied. Assessment of different microbial groups such as fungi, actinomycetes and bacteria (heterotrophic, spore forming, free-living nitrogen fixing, phosphate solubilising and cellulose degrading) from mine soils were found to be either extremely low or absent in some soil samples. Further chromium tolerant bacteria (CTB) were isolated using 100 mg/L Cr(VI) enriched nutrient agar medium and were screened for their tolerance towards increasing concentrations of hexavalent chromium and other toxic metals. Out of 23 CTB isolates, three bacteria tolerated up to 900 mg/L, 6 up to 500 mg/L, 20 up to 200 mg/L of Cr(VI). These bacteria were also found to be sensitive towards Cu > Co > Cd and very few CTB strains could show multiple metal tolerance. These strains have great scope for their application in bioremediation of toxic chromium ions in presence of other metals ions, which needs to be explored for their biotechnological applications.  相似文献   

15.
A green-coloured phyllosilicate occurring on the walls of amygdaloidal cavities and along fractures in the Deccan Flood basalts at Killari, Maharashtra, India, has been identified as iron-rich saponite with a chemical composition [Na0.60 K0.40 Ca0.47] {Mg2.05Fe3.95} (Si6.45Al1.55) O20(OH)4. In order to explore the possible application of this phyllosilicate for environmental management, we have carried out X-ray photon spectroscopic (XPS) and diffuse reflectance spectroscopic (DRS) measurements on the dichromate solutions, in both the untreated and treated form. The dichromate solution treated with the saponite samples show a remarkable capability not only to adsorb hexavalent chromium but also effect a reduction of hexavalent to trivalent chromium at an efficiency of 75%. These valence states of chromium were characterised unambiguously by XPS and DRS spectra collected at room temperature. Our studies show that Killari saponite is capable of reducing Cr (VI) to Cr (III). The ferrous saponite in Deccan Flood basalts could therefore be a useful mineral in environmental management in areas affected by Cr (VI) effluents.  相似文献   

16.
藏北班公湖—怒江缝合带中—西段康穷地区发现铬铁矿   总被引:2,自引:1,他引:1  
李兴奎  李才  王明 《地质通报》2014,33(11):1815-1819
班公湖—怒江缝合带中—西段康穷地区发育一套各端元出露比较齐全的蛇绿岩岩石组合,向东与八乌错、米素、赤日、孜如错、桑日一带的超基性岩共同构成了班公湖—怒江缝合带中—西段基性超基性岩带。2012年,于康穷地区变质橄榄岩岩体边部发现一处铬铁矿体,首次证实这一巨大的超基性岩带内存在铬铁矿。铬铁矿露头良好,地表见有2条矿体,在露头西侧还见有大片残坡积铬铁矿,残坡积之下的深部情况尚难确定。矿体以冶金级富铬矿石为主,Cr2O3含量最高可达59.11%,矿体围岩主要为方辉橄榄岩,见有少量纯橄榄岩。初步研究认为,康穷铬铁矿类型为豆荚状铬铁矿。该矿体的发现为班公湖—怒江缝合带中—西段铬铁矿的找矿工作提供了重要线索,对区域找矿具有重要的指示意义。  相似文献   

17.
<正>In the present study,we present the occurrence and emplacement of chromite ore deposits from two abandoned mines(Kankavali[Janoli]and Wagda) in the Sindhudurg district of Maharashtra,India.These ores,that occurred as lenses and are associated with metamorphic and ultrabasic rocks,consist of octahedral grains of chromite,while clinochlore is present between the interstices of these grains.The Kankavali(Janoli) and Wagda ores revealed a dominance of Cr_2O_3 followed by FeO and variable proportions of A1_2O_3,MgO,and SiO_2.The former deposits have a slightly higher Cr_2O_3(average 52 wt%) and FeO(~18 wt%) than those from Wagda(Cr_2O_3~50 wt%,FeO~25 wt%).The similar Cr~# values(0.73 for Kankavali[Janoli],0.74 for Wagda) correspond to those reported for typical podiform-type chromite deposits.We suggest that the ores were emplaced as phacoliths in folded outcrops with a steep easterly dip and a northwest-southeast trend.We postulate the continuation of the fold structure from Janoli to Wagda(~4.5 km apart) and the probable (sporadic) occurrence of chromite along this stretch.The possibility of the contribution of chromite grains from these areas to the coastal placer deposits cannot be ruled out.  相似文献   

18.
The charged sites on soil particles are important for the retention/adsorption of metals. Metallic counterions can neutralize the intrinsic charges on the surfaces of soil particles by forming complexes. In this study, efforts have been made to determine the effect of surface potential, pH, and ionic strength on the adsorption of four metal ions, hexavalent chromium Cr(VI), trivalent chromium Cr(III), nickel Ni(II) and cadmium Cd(II), in glacial till soil. Batch tests were performed to determine the effect of pH (2–12) and ionic strength (0.001–0.1 M KCl) on zeta potential of the glacial till soil. The point of zero charge (pH PZC ) of glacial till was found to be 7.0±2.5. Surface charge experiments revealed the high buffering capacity of the glacial till. Batch adsorption experiments were conducted at natural pH (8.2) using various concentrations of selected metals. The adsorption data was described by the Freundlich adsorption model. Overall glacial till shows lower adsorption affinity to Cr(VI) as compared to cationic metals, Cr(III), Ni(II) and Cd(II).  相似文献   

19.
The redox-sensitive stable isotope geochemistry of chromium bears the potential to monitor the attenuation of chromate pollution and to investigate changes in environmental conditions in the present and the past. The use of stable Cr isotope data as a geo-environmental tracer, however, necessitates an understanding of the reaction kinetics and Cr fractionation behaviour during redox transition and isotope exchange. Here, we report stable chromium isotope fractionation data for Cr(VI) reduction, Cr(III) oxidation and isotopic exchange between soluble Cr(III) and Cr(VI) in aqueous media. The reduction of Cr(VI) to Cr(III) with H2O2 under strongly acidic conditions shows a near-equilibrium isotope fractionation of Δ53/52Cr(Cr(III)-Cr(VI)) of −3.54 ± 0.35‰. At pH neutrality, however, the reduction experiments show a kinetic isotope fractionation Δ53/52Cr(Cr(III)-Cr(VI)) of −5‰ for the extent of reduction of up to 85% of the chromium. The oxidation of Cr(III) to Cr(VI) in alkaline media, using H2O2 as the oxidant, cannot be explained by a single, unidirectional reaction. Our experiments indicate that the involvement of the unstable intermediates Cr(IV) and Cr(V) and their disproportionation during redox reactions between Cr(III) and Cr(VI) influence the overall fractionation factor, depending on the prevailing pH conditions and the reaction rates. No detectable isotope exchange between soluble Cr(VI) and Cr(III) species at pH values of 5.5 and 7 was revealed over a timescale of days to weeks. This means that, at least within such a time frame, the isotopic composition of Cr(VI) in a natural system will not be influenced by equilibration with any Cr(III) and thus reveal the true extent of reduction, given that the Cr isotope composition of the source Cr(VI) and the fractionation factor for the prevailing conditions are known.  相似文献   

20.
The present study aims at searching the potential of commercial grade steel wool in reducing hexavalent chromium in aqueous phase under batch mode. About 30 % of the initial hexavalent chromium was found to reduce within 2 h at a pH of 3. However, on testing the combined effects of different process parameters, namely the solution pH, wool loading, etc., the optimum batch parametric condition has been fixed. A moving boundary type kinetic model, which takes into account the effect of passivation along with the direct reduction mechanism to simulate the gross uptake profile of Cr(VI) from the bulk solution is proposed. The effective pore diffusivity of Cr(VI) in commercial steel wool was determined by a suitable global optimization technique. Additionally, the model is also capable to simulate the decline of active external surface area of the wool caused by passivation with time. A good match of the experimental data and model-simulated transient bulk concentration of Cr(VI) (under optimum parametric condition only) establishes the general validity of the proposed model.  相似文献   

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