首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 203 毫秒
1.

Zero-valent iron (Fe0) has been widely used for Cr(VI) removal; however, the removal mechanisms of Cr(VI) from aqueous solution under complex hydrogeochemical conditions were poorly understood. In this research, the mixed materials containing cast iron and activated carbon were packed in columns for the treatment of aqueous Cr(VI)-Cr(III) in groundwater with high concentration of Ca2+, Mg2+, HCO3 , NO3 , and SO4 2−. We investigate the influences of those ions on Cr(VI) removal, especially emphasizing on the reaction mechanisms and associated precipitations which may lead to porosity loss by using X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) techniques. The results show that the precipitations accumulated on the material surface were (Fe/Cr) (oxy)hydroxide, mixed Fe(III)-Cr(III) (oxy)hydroxides, Fe2O3, CaCO3, and MgCO3. During these reactions, the Cr(VI) was reduced to Cr(III) coupled with the oxidated Fe0 to Fe(II) through the galvanic corrosion formed by the Fe0-C and/or the direct electron transfer between Fe0 and Cr(VI). In addition, Cr(VI) could be reduced by aqueous Fe(II), which dominated the whole removal efficiency. The primary aqueous Cr(III) was completely removed together with Cr(III) reduced from Cr(VI) even when Cr(VI) was detected in the effluent, which meant that the aqueous Cr(III) could occupy the adsorption sites. In general, the combined system was useful for the Cr(VI)-Cr(III) treatment based on galvanic corrosion, and the hardness ions had a negative effect on Cr(VI) removal by forming the carbonates which might promote the passivation of materials and decrease the removal capacity of the system.

  相似文献   

2.
Che H  Lee W 《Chemosphere》2011,82(8):1103-1108
Selective redox degradation of chlorinated aliphatics by Fenton reaction in pyrite suspension was investigated in a closed system. Carbon tetrachloride (CT) was used as a representative target of perchlorinated alkanes and trichloroethylene (TCE) was used as one of highly chlorinated alkenes. Degradation of CT in Fenton reaction was significantly enhanced by pyrite used as an iron source instead of soluble Fe. Pyrite Fenton showed 93% of CT removal in 140 min, while Fenton reaction with soluble Fe(II) showed 52% and that with Fe(III) 15%. Addition of 2-propanol to the pyrite Fenton system significantly inhibited degradation of TCE (99% to 44% of TCE removal), while degradation of CT was slightly improved by the 2-propanol addition (80-91% of CT removal). The result suggests that, unlike oxidative degradation of TCE by hydroxyl radical in pyrite Fenton system, an oxidation by the hydroxyl radical is not a main degradation mechanism for the degradation of CT in pyrite Fenton system but a reductive dechlorination by superoxide can rather be the one for the CT degradation. The degradation kinetics of CT in the pyrite Fenton system was decelerated (0.13-0.03 min−1), as initial suspension pH decreased from 3 to 2. The formation of superoxide during the CT degradation in the pyrite Fenton system was observed by electron spin resonance spectroscopy. The formation at initial pH 3 was greater than that at initial pH 2, which supported that superoxide was a main reductant for degradation of CT in the pyrite Fenton system.  相似文献   

3.
Iron isotope compositions of various Fe pools in aquifer sediments were measured at a known As-contaminated site in the Datong Basin, China. The δ56Fe values of HCl-extracted poor-crystalline Fe(III) range widely from ?0.41‰ to 0.36‰. We interpret the low Fe(II)/FeExtractable ratios (<50%) and the negative correlation between Fe(II)/FeExtractable and δ56Fe values in HCl-extracted poor-crystalline Fe to be best explained by redox cycling of Fe induced by microbial Fe(III) reduction. However, the high Fe(II)/FeExtractable ratios (?70%) and positive correlation between Fe(II)/FeExtractable and δ56Fe values for HCl-extracted poor-crystalline Fe indicates production of sulfides (FeSs). The δ56Fe values of crystalline Fe(III) extracted by reductant appears to be comparatively small varying from ?0.01‰ to 0.24‰, which is consistent with the δ56Fe values for ferric oxides/hydroxides having undergone microbial Fe(III) reduction. The Fe isotope composition of various Fe pools shows the transformation between crystalline Fe(III) and poor-crystalline crystalline Fe(III) and the secondary Fe(II) phases has already occurred or is occurring in aquifer sediments. More importantly, there is a significant difference in the As concentrations in crystalline Fe(III) oxides/hydroxides and HCl-extracted Fe phases. The concentrations of As range from 1.6 to 29.9 mg kg?1 and from 0.6 to 3.0 mg kg?1, for crystalline Fe(III) and HCl-extracted Fe phases respectively. Accordingly, the transformation of Fe minerals induced by microbial Fe(III) reduction can contribute to the mobilization of As. This study is the first to examine the Fe isotope compositions in high As aquifer sediments; the results show that the Fe isotope would be an important tool in demonstrating the enrichment of As in groundwater.  相似文献   

4.
Liang C  Bruell CJ  Marley MC  Sperry KL 《Chemosphere》2004,55(9):1213-1223
The objective of the laboratory study is to examine the conditions under which transition metal ions (e.g., ferrous ion, Fe2+) could activate the persulfate anion (S2O8(2)-) to produce a powerful oxidant known as the sulfate free radical (SO4-*) with a standard redox potential of 2.6 V. The SO4-* is capable of destroying groundwater contaminants in situ such as trichloroethylene (TCE). Experiments using Fe2+ as an activator under various molar ratios of S2O8(2)-/Fe2+/TCE in an aqueous system indicated that partial TCE degradation occurred almost instantaneously and then the reaction stalled. Either destruction of SO4-* in the presence of excess Fe2+ or the rapid conversion of all Fe2+ to Fe3+ limited the ultimate oxidizing capability of the system. Sequential addition of Fe2+ in small increments resulted in an increased TCE removal efficiency. Therefore, it appeared that Fe2+ played an important role in generating SO4-*. An observation of oxidation-reduction potential (ORP) variations revealed that the addition of sodium thiosulfate (Na2S2O3) to the ferrous ion activated persulfate system could significantly decrease the strong oxidizing conditions. It was hypothesized that the thiosulfate induced reducing conditions might convert Fe3+ to a lower valence state of Fe2+, making the Fe2+ available to activate persulfate decomposition. The sequential addition of thiosulfate (S2O3(2)-), after the initial stalling of ferrous ion activated persulfate oxidation of TCE, resulted in an improvement in TCE removal. The ferrous ion activated persulfate-thiosulfate redox couple resulted in fairly complete TCE degradation in aqueous systems in a short time frame. In soil slurry systems, TCE degradation was slower in comparison to aqueous systems.  相似文献   

5.
The influence of dissolved NO2 and iron on the oxidation rate of S(IV) species in the presence of dissolved oxygen is presented. To match the conditions in the real environment, the concentration of iron in the reaction solution and trace gases in the gas mixture was typical for a polluted atmosphere. The time dependence of HSO3, SO42−, NO2 and NO3 and the concentration ratio between Fe(II) and total dissolved iron were monitored. Sulphate formation was the most intensive in the presence of an SO2/NO2/air gas mixture and Fe(III) in solution. The highest contribution to the overall oxidation was from Fe-catalysed S(IV) autoxidation. The reaction rate in the presence of both components was equal to the sum of the reaction rates when NO2 and Fe(III) were present separately, indicating that under selected experimental conditions there exist two systems: SO2/NO2/air and SO2/NO2/air/Fe(III), which are unlikely to interact with each other. The radical chain mechanism can be initiated via reactions Fe(III)–HSO3 and NO2–SO32−/HSO3.  相似文献   

6.

CoFe2O4/ordered mesoporous carbon (OMC) nanocomposites were synthesized and tested as heterogeneous peroxymonosulfate (PMS) activator for the removal of rhodamine B. Characterization confirmed that CoFe2O4 nanoparticles were tightly bonded to OMC, and the hybrid catalyst possessed high surface area, pore volume, and superparamagnetism. Oxidation experiments demonstrated that CoFe2O4/OMC nanocomposites displayed favorable catalytic activity in PMS solution and rhodamine B degradation could be well described by pseudo-first-order kinetic model. Sulfate radicals (SO4 ·) were verified as the primary reactive species which was responsible for the decomposition of rhodamine B. The optimum loading ratio of CoFe2O4 and OMC was determined to be 5:1. Under optimum operational condition (catalyst dosage 0.05 g/L, PMS concentration 1.5 mM, pH 7.0, and 25 °C), CoFe2O4/OMC-activated peroxymonosulfate system could achieve almost complete decolorization of 100 mg/L rhodamine B within 60 min. The enhanced catalytic activity of CoFe2O4/OMC nanocomposites compared to that of CoFe2O4 nanoparticles could be attributable to the increased adsorption capacity and accelerated redox cycles between Co(III)/Co(II) and Fe(III)/Fe(II).

  相似文献   

7.
8.

Sulfamethoxazole (SMX) was decomposed by using gamma irradiation in the presence of different additives such as NO3 , NO2 , Cr(VI), 2-propanol, and tert-butanol. The results demonstrated that NO3 , NO2 , 2-propanol, and tert-butanol inhibited SMX radiolytic removal. However, there existed a synergetic effect for radiolytic removal of the mixture containing SMX and Cr(VI). At an absorbed dose of 150 Gy, the removal percentages of SMX and Cr(VI) in the mixture were 73.5 and 84.6%, respectively, which was higher than the removal percentages of 70.6 and 4.1% for the single component of SMX and Cr(VI). This provides us an insight into treating the combined pollution in micro-polluted water. The SMX radiolytic removal followed a pseudo first-order reaction kinetic model, and the rate constant ratios of ·OH, eaq , and H· towards SMX radiolysis were 10.4:1:2.9. In addition, 24-h bio-inhibitory to the macroalgae of SMX solution during gamma irradiation reached the maximum of 0.85 at an adsorbed dose of 100 Gy, then gradually decreased with the increasing adsorbed dose. Based on LC-MS analysis and quantum chemical calculation, the degradation intermediates were determined and concluded that SMX radiolytic removal was mainly via ·OH radical attack and direct decomposition of SMX molecule by gamma ray.

  相似文献   

9.
The ability of free ferrous ion activated persulfate (S2O82−) to generate sulfate radicals (SO4) for the oxidation of trichloroethylene (TCE) is limited by the scavenging of SO4 with excess Fe2+ and a quick conversion of Fe2+ to Fe3+. This study investigated the applicability of ethylene-diamine-tetra-acetic acid (EDTA) chelated Fe3+ in activating persulfate for the destruction of TCE in aqueous phase under pH 3, 7 and 10. Fe3+ and EDTA alone did not appreciably degrade persulfate. The presence of TCE in the EDTA/Fe3+ activated persulfate system can induce faster persulfate and EDTA degradation due to iron recycling to activate persulfate under a higher pH condition. Increasing the pH leads to increases in pseudo-first-order-rate constants for TCE, S2O82− and EDTA degradations, and Cl generation. Accordingly, the experiments at pH 10 with different EDTA/Fe3+ molar ratios indicated that a 1/1 ratio resulted in a remarkably higher degradation rate at the early stage of reaction as compared to results by other ratios. Higher persulfate dosage under the EDTA/Fe3+ molar ratio of 1/1 resulted in greater TCE degradation rates. However, increases in persulfate concentration may also lead to an increase in the rate of persulfate consumption.  相似文献   

10.
Experiments were conducted to assess the impact of citric acid (CA) and rhizosphere bacteria on metal uptake in Phragmites australis cultured in a spiked acid mine drainage (AMD) soil. Rhizosphere iron-oxidizing bacteria (Fe(II)OB) enhanced the formation of Fe plaque on roots, which decreased the uptake of Fe and Mn. CA inhibited the growth of Fe(II)OB, decreased the formation of metal plaque, raised the metal mobility in soil, and increased the accumulation of metals in all tissues of the reeds. The higher the CA dosage, the more metals accumulated into reeds. The total amount of metals in reeds increased from 7.8?±?0.5?×?10?6 mol plant?1 (Mn), 1.4?±?0.1?×?10?3 mol plant?1 (Fe), and 1.0?±?0.1?×?10?4 mol plant?1 (Al) in spiked soil without CA to 22.2?±?0.5?×?10?6 mol plant?1 (Mn), 3.5?±?0.06?×?10?3 mol plant?1 (Fe), and 5.0?±?0.2?×?10?4 mol plant?1 (Al) in soil added with 33.616 g C6H8O7·H2O for per kilogram soil. CA could be effective at enhancing the phytoremediation of metals from AMD-contaminated soil.  相似文献   

11.
Dong H  Guan X  Wang D  Li C  Yang X  Dou X 《Chemosphere》2011,85(7):1115-1121
Batch experiments were carried out to investigate the influences of H2O2/Fe(II) molar ratio, pH, sequence of pH adjustment, initial As(V) concentration, and interfering ions on As(V) removal in H2O2-Fe(II) process from synthetic acid mine drainage (AMD). The optimum H2O2/Fe(II) molar ratio was one for arsenate removal over the pH range of 4-7. Arsenate removal at pH 3 was poor even at high Fe(II) dosage due to the high solubility of Fe(III) formed in situ. With the increase of Fe(II) dosage, arsenate removal increased progressively before a plateau was reached at pH 5 as arsenate concentration varied from 0.05 to 2.0 mg L−1. However, arsenate removal was negligible at Fe/As molar ratio <3 and then experienced a striking increase before a plateau was reached at pH 7 and arsenate concentration ≥1.0 mg L−1. The co-occurring ions exerted no significant effect on arsenate removal at pH 5. The experimental results with synthetic AMD revealed that this method is highly selective for arsenate removal and the co-occurring ions either improved arsenate removal or slightly depressed arsenate removal at pH 5-7. The extended X-ray absorption fine structure (EXAFS) derived As-Fe length, 3.27-3.30 Å, indicated that arsenate was removed by forming bidentate-binuclear complexes with FeO(OH) octahydra. The economic analysis revealed that the cost of the H2O2-Fe(II) process was only 17-32% of that of conventional Fe(III) coagulation process to achieve arsenate concentration below 10 μg L−1 in treated solution. The results suggested that the H2O2-Fe(II) process is an efficient, economical, selective and practical method for arsenate removal from AMD.  相似文献   

12.
13.

Singlet oxygen (1O2), hydroxyl radicals (OH), and excited triplet states of organic matter (3OM*) play a key role in the degradation of pollutants in aquatic environments. The formation rates and quantum yields (Φ) of these reactive intermediates (RI) through photosensitized reactions of dissolved organic matter (DOM) have been reported in the literature for decades. Urban biowaste-derived substances (UW-BOS), a form of organic matter derived from vegetative and urban waste, have recently been shown to be efficient sensitizers in the photo-degradation of different contaminants. Nevertheless, no quantitative measurements of photo-oxidant generation by UW-BOS have been reported. In this study, the formation quantum yields of 1O2 and OH, as well as quantum yield coefficients of TMP degradation (indicative of 3OM* formation), were quantified for two UW-BOS samples, under 254-nm UV radiation or simulated sunlight and compared to a DOM standard from the Suwanee River (SRNOM). Values of Φ for UW-BOS samples ranged from Φ(+1O2) = 8.0 to 8.8 × 10−3, Φ(+OH) = 4.1 to 4.3 × 10−6, and f TMP = 1.22 to 1.23 × 102 L Einstein−1 under simulated sunlight and from Φ(+1O2) = 1.4 to 2.3 × 10−2, Φ(+OH) = 1.3 to 3.5 × 10−3, and f TMP = 3.3 to 3.9 × 102 L Einstein−1 under UV. Although UW-BOS are not necessarily better than natural DOM regarding photosensitizing properties, they do sensitize the production of RI and could potentially be used in engineered treatment systems.

  相似文献   

14.
Most studies on the treatment of chlorinated contaminants by Fe(0) focus on aqueous system tests. However, few is known about the effectiveness of these tests for degrading chlorinated contaminants such as 1,1,1-trichloroethane (TCA) in soil. In this work, the reductive degradation performance of 1,1,1-TCA by Fe(0) was thoroughly investigated in a soil slurry system. The effects of various factors including acid-washed iron, the initial 1,1,1-TCA concentration, Fe(0) dosage, slurry pH, and common constituents in groundwater and soil such as Cl?, HCO3 ?, SO4 2?, and NO3 ? anions and humic acid (HA) were evaluated. The experimental results showed that 1,1,1-TCA could be effectively degraded in 12 h for an initial Fe(0) dosage of 10 g L?1 and a soil/water mass ratio of 1:5. The soil slurry experiments showed two-stage degradation kinetics: a slow reaction in the first stage and a fast reductive degradation of 1,1,1-TCA in the second stage. The reductive degradation of 1,1,1-TCA was expedited as the mass concentration of Fe(0) increased. In addition, high pHs adversely affected the degradation of 1,1,1-TCA over a pH range of 5.4–8.0 and the reductive degradation efficiency decreased with increasing slurry pH. The initial 1,1,1-TCA concentration and the presence of Cl? and SO4 2? anions had negligible effects. HCO3 ? anions had a accelerative effect on 1,1,1-TCA removal, and both NO3 ? and HA had inhibitory effects. A Cl? mass balance showed that the amount of Cl? ions released into the soil slurry system during the 1,1,1-TCA degradation increased with increasing reaction time, suggesting that the main degradation mechanism of 1,1,1-TCA by Fe(0) in a soil slurry system was reductive dechlorination with 1,1-DCA as the main intermediate. In conclusion, this study provides a theoretical basis for the practical application of the remediation of contaminated sites containing chlorinated solvent.  相似文献   

15.
Jung B  Batchelor B 《Chemosphere》2008,71(4):726-734
Transformation of 1,1,2,2-tetrachloroethane (1,1,2,2-TeCA) by Fe(II) in 10% cement slurries was characterized using a batch reactor system. 1,1,2,2-TeCA was completely converted to trichloroethylene (TCE) within 1h in all experiments, even in controls with cement that did not include Fe(II). Therefore, complete degradation of 1,1,2,2-TeCA depends on the behavior of TCE. The half-life of TCE was observed to be 15d when concentrations of Fe(II) and 1,1,2,2-TeCA were 98mM and 0.245mM, respectively. The kinetics of TCE removal was observed to be dependent on Fe(II) dose, pH and initial substrate concentration. Pseudo-first-order rate constants linearly increased with Fe(II) dose up to 198mM when initial target concentration was 0.245mM. Pseudo-first-order kinetics generally described the degradation reactions of TCE at a specific initial concentration, but a modified Langmuir-Hinshelwood model was necessary to describe the degradation kinetics of TCE over a wide range of initial concentrations. A surface reaction of TCE on active solids, which were formed from Fe(II) and products of cement hydration appears to control observed TCE degradation kinetics.  相似文献   

16.
This study aims to develop a high-efficiency radical oxidation process for enhancing the dewaterability of waste activated sludge (WAS). Radical scavenging studies combined with electron paramagnetic resonance (EPR) were carried out for the direct radical identification and effectiveness evaluation of radical oxidation. The results indicated that Fe(II)-activated CaO2 can pose a superior effect on dewatering WAS due to its distinctive capacity of stable ?OH production and the high reaction efficiency of regulated-released ?OH with water-holding organics. The mechanism for the enhanced dewatering performance was also explored. The rupture of sludge colloidal flocs and the reduction of hydrophilic functional groups in loosely bound extracellular polymeric substances (LB-EPS) were found to be mainly responsible for the release of interstitial water and improved dewaterability, respectively. In addition, an inference about the relationship between interfacial water and zeta potential of different EPS fractions was established by the simultaneous measurement of the binding affinities of Ca2+ and Fe2+/Fe3+ for EPS and bound water content. All these results provide the direct evidence that Fe(II)-activated CaO2 is a promising pretreatment reagent for sludge disposal.

Implications: Fe(II)-activated CaO2 was first proposed to be highly effective in enhancing the dewaterability of waste activated sludge. Electron paramagnetic resonance (EPR) spectroscopy provided the direct evidence for the specific advantages of CaO2, especially the capacity of durable and efficacious ?OH production leading to the excellent conditioning performance.  相似文献   

17.
The rate constants for reactions of the SO4 radical anion with some low molecular weight monocarboxylic acids (MCAs) and dicarboxylic acids (DCAs) and their anions using the laser flash photolysis-long path laser absorption (LFP-LPLA) technique were determined. The present study contains the first measured rate constants for SO4 reactions with glycolic, lactic, malic and malonic acid. The rate constants are found to be in the range from 105 to 107 M−1 s−1, with the lower values found for acids and higher values for their respective anions. In addition, the rate constants for scavenging of SO4 by all investigated organics in the Mn(II)-catalyzed S(IV) autoxidation at pH 4.5 and T=25 °C were determined by means of the reversed rate method. The comparison between these rate constants and the rate constants obtained by direct measurements confirms the proposed inhibiting mechanism for the Mn(II)-catalyzed S(IV) autoxidation in the presence of monocarboxylic acids. In the case of formic acid, which causes the highest inhibition, this mechanism can explain the second part of kinetic traces (i.e. after the induction period). Surprisingly, although dicarboxylic acids are reactive toward SO4 they do not contribute to the inhibition of S(IV) oxidation (especially malic and malonic acids).  相似文献   

18.
As a part of a study developing a biological reactive barrier system to treat nitrate-contaminated groundwater, the effects of reactive media composition and co-contaminants on sulfur-oxidizing autotrophic denitrification were investigated. The size of sulfur granules affected the denitrification rates; kinetic constants of 2.883, 2.949, and 0.677 mg-N(1/2)/L(1/2)/day were obtained when the granule sizes were below 2 mm, between 2 and 5 mm, and over 5 mm, respectively. When the volume ratios of sulfur to limestone were 1:1, 2:1, 3:1, and 4:1, kinetic constants of 5.490, 3.903, 4.072, and 2.984 mg-N(1/2)/L(1/2)/day were obtained, respectively. The presence of TCE up to 20 mg/L didn't significantly affect nitrate removal efficiency. At the TCE concentration of 80 mg/L, however, nitrate removal was markedly inhibited. Also, Zn and Cu inhibited the denitrification activity at more than 0.5 mg/L of concentration whereas Cr (VI) did not significantly affect the nitrate removal efficiency at all levels tested.  相似文献   

19.
Increasing attention has been paid to pyrite due to its ability to generate hydroxyl radicals in air-saturated solutions. In this study, the mineral pyrite was studied as a catalyst to activate molecular oxygen to degrade Acid Orange 7 (AO7) in aqueous solution. A complete set of control experiments were conducted to optimize the reaction conditions, including the dosage of pyrite, the AO7 concentration, as well as the initial pH value. The role of reactive oxygen species (ROS) generated by pyrite in the process was elucidated by free radical quenching reactions. Furthermore, the concentrations of Fe(II) and total Fe formed were also measured. The mechanism for the production of ROS in the pyrite/H2O/O2 system was that H2O2 was formed by hydrogen ion and superoxide anion (O2 ·?) which was produced by the reaction of pyrite activating O2 and then reacted with Fe(II) dissolved from pyrite to produce ·OH through Fenton reaction. The findings suggest that pyrite/H2O/O2 system is potentially practical in pollution treatment. Moreover, the results provide a new insight into the understanding of the mechanism for degradation of organic pollutants by pyrite.  相似文献   

20.

The response of soil respiration (Rs) to nitrogen (N) addition is one of the uncertainties in modelling ecosystem carbon (C). We reported on a long-term nitrogen (N) addition experiment using urea (CO(NH2)2) fertilizer in which Rs was continuously measured after N addition during the growing season in a Chinese pine forest. Four levels of N addition, i.e. no added N (N0: 0 g N m−2 year−1), low-N (N1: 5 g N m−2 year−1), medium-N (N2: 10 g N m−2 year−1), and high-N (N3: 15 g N m−2 year−1), and three organic matter treatments, i.e. both aboveground litter and belowground root removal (LRE), only aboveground litter removal (LE), and intact soil (CK), were examined. The Rs was measured continuously for 3 days following each N addition application and was measured approximately 3–5 times during the rest of each month from July to October 2012. N addition inhibited microbial heterotrophic respiration by suppressing soil microbial biomass, but stimulated root respiration and CO2 release from litter decomposition by increasing either root biomass or microbial biomass. When litter and/or root were removed, the “priming” effect of N addition on the Rs disappeared more quickly than intact soil. This is likely to provide a point of view for why Rs varies so much in response to exogenous N and also has implications for future determination of sampling interval of Rs measurement.

  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号