Electrochemical regeneration of Fe2+ in Fenton oxidation processes

This study is to establish optimal conditions for the minimization of iron sludge produced in Fenton oxidation processes by electro-regenerating Fe(2+) with constant potential (CPM) or constant current mode (CCM). Results indicate that the optimal cathodic potential for Fe(2+) regeneration is -0.1 V vs. the saturated calomel electrode (SCE) in terms of current efficiency. Keeping the initial Fe(3+) concentration ([Fe(3+)](0)) constant, the average current density produced at -0.1 V vs. SCE (CPM) is approximately equal to the optimal current density applied in the CCM. The suitable pH range is below the pH value determined by Fe(3+) hydrolysis. As expected, increasing cathode surface area and solution temperature notably increases Fe(2+) regeneration rate. At the optimal potential, the average current density increases linearly with [Fe(3+)](0), exhibiting a slope of 8.48 x 10(-3)(A/m(2))(mg/L)(-1). The average current efficiency varies with [Fe(3+)](0), e.g., 75% and 96-98% at 100 and > or = 500 mg/L [Fe(3+)](0), respectively. Once reaching 75% of Fe(2+) regeneration capacity, further regeneration becomes difficult due to Fe(3+) mass transfer limitation. Fe(2+) can also be effectively regenerated by dissolving iron sludge at low pH (usually 相似文献   

Effects of iron surface pretreatment on sorption and reduction kinetics of trichloroethylene in a closed batch system

The decline of trichloroethylene (TCE) in a metallic iron-water system results from the combination of reduction reaction and sorption onto iron surfaces. Sorption, particularly by highly impure iron, accelerates the removal of TCE from the aqueous phase, but delays the prevalence of steady-state conditions. In this case, an overly high value of reaction rate constant in the design of a treatment system would be used. In this work, the effects of an iron surface with 8.0% C, 6.1% O and 0.8% Si separately following HCl-washing and H2-reducing pretreatment on sorption and reduction rates were examined. The amounts of both aqueous and sorbed TCE were measured using a modified solvent-extraction method. TCE sorption onto an iron surface, as quantified by the Langmuir sorption maximum, followed the trend H2-reduced Fe0 > HCl-washed Fe0 > untreated Fe0 (0.887, 0.365 and 0.311 mg/g, respectively). Measurements of the concentration of sorbed TCE revealed that about 34-37% of the initial mass of TCE in the aqueous phase was removed by sorption by H2-reduced Fe0, 16-19% was removed by HCl-washed Fe0 and 13-16% was removed by untreated Fe0. A combination of new and previously reported data on cast iron's capacity to sorb TCE revealed a linear relationship between this capacity and the C fraction in the surface of the iron, with the coefficient of determination (r2) exceeding 0.99. The first-order observed rate constants (k(obs)) of the reduction of TCE in contact with Fe0 were obtained from the slope of a plot of total TCE loss rate (-dC(T)/dt) versus the amount of TCE in the aqueous phase (C(w)) using linear least-squares analysis. The k(obs) values were 0.080, 0.148 and 0.191 h(-1) for untreated, HCl-washed and H2-reduced Fe0, respectively. Normalized to iron surface area concentration, the specific rate constants (k(SA)) were 2.3 7x 10(-3) , 2.31 x 10(-3) and 5.62 x 10(-3) h(-1) m(-2) L, respectively. The results indicated that HCl-washing approximately doubled k(obs), primarily because of the increase in the surface area of the iron, and it slightly decreased k(SA) due to rapid corrosion during the rinsing process. Both the number of reactive sites and the sorption capacity per unit iron surface area through the H2-reducing pretreatment were increased due to the reduction of iron oxide layer and the carbonization of carbon-containing subjects on the iron's surface. Hence, the H2 reduction of cast iron promotes the removal of TCE from contaminated water by the concurrent sorption and reduction.     

Study on Fe(VI) species as a disinfectant: quantitative evaluation and modeling for inactivating Escherichia coli

Ferrate (Fe(VI)) has high potentials as a multi-purpose water treatment chemical acting as an oxidant, coagulant, and disinfectant, but little detail has been reported concerning its biocidal ability. In this study, the inactivation efficiencies of three Fe(VI) species (H(x)FeO(4)(x-2), x=0, 1, 2) are quantified using Escherichia coli as a model microorganism. E. coli inactivation by Fe(VI) was performed in solutions buffered with 25 mM phosphate in the pH range of 5.6-8.2 and at 25 degrees C. Kinetics of E. coli inactivation were successfully fitted to the Modified Delayed Chick-Watson model in the tested pH range, indicating that log inactivation level of E. coli is linearly proportional to exposure amount of E. coli to Fe(VI). The rate constant of E. coli inactivation by Fe(VI) (k(obs)) that was obtained from the linear regression increased non-linearly from 0.33 to 6.25 l(mg min)(-1) with decreasing pH from 8.2 to 5.6. From the measured pH dependency of k(obs) and the known acidity constants of Fe(VI) species (pK(a), H(2)FeO(4)=3.50 and pK(a), HFeO(4)(-)=7.23), HFeO(4)(-) and H(2)FeO(4) were found to be 3 and 265 times as effective as FeO(4)(2-) in E. coli inactivation, respectively.     

Intraparticle diffusion and adsorption of arsenate onto granular ferric hydroxide (GFH)

Porous iron oxides are being evaluated and selected for arsenic removal in potable water systems. Granular ferric hydroxide, a typical porous iron adsorbent, is commercially available and frequently considered in evaluation of arsenic removal methods. GFH is a highly porous (micropore volume approximately 0.0394+/-0.0056 cm(3)g(-1), mesopore volume approximately 0.0995+/-0.0096 cm(3)g(-1)) adsorbent with a BET surface area of 235+/-8 m(2)g(-1). The purpose of this paper is to quantify arsenate adsorption kinetics on GFH and to determine if intraparticle diffusion is a rate-limiting step for arsenic removal in packed-bed treatment systems. Data from bottle-point isotherm and differential column batch reactor (DCBR) experiments were used to estimate Freundlich isotherm parameters (K and 1/n) as well as kinetic parameters describing mass transfer resistances due to film diffusion (k(f)) and intraparticle surface diffusion (D(s)). The pseudo-equilibrium (18 days of contact time) arsenate adsorption density at pH 7 was 8 microg As/mg dry GFH at a liquid phase arsenate concentration of 10 microg As/L. The homogeneous surface diffusion model (HSDM) was used to describe the DCBR data. A non-linear relationship (D(S)=3.0(-9) x R(p)(1.4)) was observed between D(s) and GFH particle radius (R(P)) with D(s) values ranging from 2.98 x 10(-12) cm(2)s(-1) for the smallest GFH mesh size (100 x 140) to 64 x 10(-11) cm(2)s(-1) for the largest GFH mesh size (10 x 30). The rate-limiting process of intraparticle surface diffusion for arsenate adsorption by porous iron oxides appears analogous to organic compound adsorption by activated carbon despite differences in adsorption mechanisms (inner-sphere complexes for As versus hydrophobic interactions for organic contaminants). The findings are discussed in the context of intraparticle surface diffusion affecting packed-bed treatment system design and application of rapid small-scale column tests (RSSCTs) to simulate the performance of pilot- or full-scale systems at the bench-scale.     

Kinetics and mechanisms of DMSO (dimethylsulfoxide) degradation by UV/H(2)O(2) process

The objective of this study was to elucidate the degradation pathways of dimethylsulfoxide (DMSO) during its mineralization caused by UV/H(2)O(2) treatment. In order to accomplish this, we measured the concentration time-profiles of DMSO and its degradation intermediates during the UV/H(2)O(2) treatment. In addition, we proposed a kinetic model that could account for the degradation pathways of DMSO during its UV/H(2)O(2) treatment. The results show that the degradation of DMSO by the UV/H(2)O(2) treatment can be classified into two major pathways, and this is supported by both the analysis of the intermediates and total organic carbon (TOC) measurements. Firstly, DMSO was degraded into sulfate (SO(4)(2-)) through the formation of methansulfinate (CH(3)SO(2)(-)) and methansulfonate (CH(3)SO(3)(-)) as sulfur-containing intermediates. One of the two carbon constituents of DMSO was highly resistant to mineralization, due to the formation of methansulfonate, which reacted very slowly with (.-)OH k = 0.8 x 10(7) M(-1)s(-1)). Secondly, the other carbon constituent of DMSO was relatively easily mineralized through the formation of formaldehyde (HCHO) and formate (HCO(2)(-)) as non-sulfur-containing intermediates. The kinetic model proposed in this study for the degradation of DMSO by (.-)OH in the UV/H(2)O(2) process was able to successfully predict the patterns of concentration time-profiles of all components during the UV/H(2)O(2) treatment of DMSO.     

Oxidative-coupling reaction of TNT reduction products by manganese oxide

Abiotic transformation of TNT reduction products via oxidative-coupling reaction was investigated using Mn oxide. In batch experiments, all the reduction products tested were completely transformed by birnessite, one of natural Mn oxides present in soil. Oxidative-coupling was the major transformation pathway, as confirmed by mass spectrometric analysis. Using observed pseudo-first-order rate constants with respect to birnessite loadings, surface area-normalized specific rate constants, ksurf, were determined. As expected, ksurf of diaminonitrotoluenes (DATs) (1.49-1.91L/m2 d) are greater about 2 orders than that of dinitroaminotoluenes (DNTs) (1.15 x 10(-2)-2.09 x 10(-2)L/m2d) due to the increased number of amine group. In addition, by comparing the value of ksurf between DNTs or DATs, amine group on ortho position is likely to be more preferred for the oxidation by birnessite. Although cross-coupling of TNT in the presence of various mediator compounds was found not to be feasible, transformation of TNT by reduction using Fe0 followed by oxidative-coupling using Mn oxide was efficient, as evaluated by UV-visible spectrometry.     

Fenton-like oxidation of 2,4,6-trinitrotoluene using different iron minerals

Degradation of 2,4,6-trinitrotoluene (TNT) was investigated in presence of different oxidants (Fenton's reagent, sodium persulfate, peroxymonosulfate and potassium permanganate) and different iron minerals (ferrihydrite, hematite, goethite, lepidocrocite, magnetite and pyrite) either in aqueous solution or in soil slurry systems. Fenton's reagent was the only oxidant able to degrade TNT in solution (k(app)=0.0348 min(-1)). When using iron oxide as heterogeneous catalyst at pH 3, specific reaction rate constants per surface area were k(surf)=1.47.10(-3) L min(-1) m(-2) and k(surf)=0.177 L min(-1) m(-2) for magnetite and pyrite, respectively while ferric iron minerals were inefficient for TNT degradation. The major asset of iron mineral catalyzed Fenton-like treatment has been the complete oxidation of the pollutant avoiding the accumulation of possible toxic by-products. In soil slurry systems, 38% abatement of the initial TNT concentration (2 g/kg) was reached after 24 h treatment time at neutral pH. Rate limiting steps were the availability of soluble iron at neutral pH together with desorption of the TNT fraction sorbed on the clay mineral surfaces.     

Oxidation of suspected N-nitrosodimethylamine (NDMA) precursors by ferrate (VI): kinetics and effect on the NDMA formation potential of natural waters

The potential of ferrate (Fe(VI)) oxidation to remove N-nitrosodimethylamine (NDMA) precursors during water treatment was assessed. Apparent second-order rate constants (k(app)) for the reactions of NDMA and its suspected precursors (dimethylamine (DMA) and 7 tertiary amines with DMA functional group) with Fe(VI) were determined in the range of pH 6-12. Four model NDMA precursors (dimethyldithiocarbamate, dimethylaminobenzene, 3-(dimethylaminomethyl)indole and 4-dimethylaminoantipyrine) showed high reactivity toward Fe(VI) with k(app) values at pH 7 between 2.6 x 10(2) and 3.2 x 10(5)M(-1)s(-1). The other NDMA precursors (DMA, trimethylamine, dimethylethanolamine, dimethylformamide) and NDMA had k(app) values ranging from 0.55 to 9.1M(-1)s(-1) at pH 7. In the second part of the study, the NDMA formation potentials (NDMA-FP) of the model NDMA precursors and natural waters were measured with and without pre-oxidation by Fe(VI). For most of the NDMA precursors with the exception of DMA, a significant reduction of the NDMA-FP (>95%) was observed after complete transformation of the NDMA precursor. This result was supported by low yields of DMA from the Fe(VI) oxidation of tertiary amine NDMA precursors. Pre-oxidation of several natural waters (rivers Rhine, Neckar and Pfinz) with a high dose of Fe(VI) (0.38 mM = 21 mg L(-1) as Fe) led to removals of the NDMA-FP of 46-84%. This indicates that the NDMA precursors in these waters have a low reactivity toward Fe(VI) because it has been shown that for fast-reacting NDMA precursors Fe(VI) doses of 20 microM (1.1 mg L(-1) as Fe) are sufficient to completely oxidize the precursors.     

Kinetics of triclosan oxidation by aqueous ozone and consequent loss of antibacterial activity: relevance to municipal wastewater ozonation

Oxidation of the antimicrobial agent triclosan by aqueous ozone (O(3)) was investigated to determine associated reaction kinetics, reaction site(s), and consequent changes in antibacterial activity of triclosan. Specific second-order rate constants, k(O(3)), were determined for reaction of O(3) with each of triclosan's acid-base species. The value of k(O(3)) determined for neutral triclosan was 1.3(+/-0.1)x10(3)M(-1)s(-1), while that measured for anionic triclosan was 5.1(+/-0.1)x10(8)M(-1)s(-1). Consequently, triclosan reacts very rapidly with O(3) at circumneutral pH (the pH-dependent, apparent second-order rate constant, K(app,O(3)) , is 3.8x10(7)M(-1)s(-1) at pH 7). The pH-dependence of K(app,O(3)) and comparison of triclosan reactivity toward O(3) with that of other phenolic compounds indicates that O(3) reacts initially with triclosan at the latter's phenol moiety. k(O(3)) values for neutral and anionic triclosan were successfully related to phenol ring substituent effects via Brown-Okamoto correlation with other substituted phenols, consistent with electrophilic attack of the triclosan phenol ring. Biological assay of O(3)-treated triclosan solutions indicates that reaction with O(3) yields efficient elimination of triclosan's antibacterial activity. In order to evaluate the applicability of these observations to actual wastewaters, triclosan oxidation was also investigated during ozonation of effluent samples from two conventional wastewater treatment plants. Nearly 100% triclosan depletion was achieved for a 4 mg/L(8.3x10(-5)mol/L)O(3) dose applied to a wastewater containing 7.5 mg/L of DOC, and approximately 58% triclosan depletion for dosage of 6 mg/L(1.3x10(-4)mol/L)O(3) to a wastewater containing 12.4 mg/L of DOC. At O(3) doses greater than 1mg/L(2.1x10(-5)mol/L), hydroxyl radical reactions accounted for <35% of observed triclosan losses in these wastewaters, indicating that triclosan oxidation was due primarily to the direct triclosan-O(3) reaction. Thus, ozonation appears to present an effective means of eliminating triclosan's antibacterial activity during wastewater treatment.     

Factors influencing inactivation of Klebsiella pneumoniae by chlorine and chloramine

Inactivation of Klebsiella pneumoniae cultures by chlorine and chloramine was evaluated under different growth conditions by varying nutrient media dilution, concentrations of essential inorganic nutrients (FeCl3, MgSO4, phosphate, and ammonium salts), and temperature. All inactivation assays were performed at room temperature (22-23 degrees C) and near neutral pH (7.2-7.5). C*T(99.9) values for chlorine increased >20-fold and for chloramine increased 2.6-fold when cells were grown in 100-fold diluted nutrient broth (2NB) solutions (final TOC of 35-40 mg/L). Background levels of Mg: 6.75 x 10(-2) mM and Fe: 3.58 x 10(-5) mM or high levels of FeCl3 (0.01 mM) and MgSO4 (1 mM) during growth resulted in the highest resistances to chlorine with C*T(99.9) values of 13.06 (+/-0.91) and 13.78 (+/-1.97) mg-min/L, respectively. Addition of low levels of FeCl3 (0.001 mM) and MgSO4 (0.1 mM) to K. pneumoniae cultures during growth resulted in the lowest bacterial resistances to inactivation; C*T(99.9) values ranged from 0.28 (+/-0.06) to 1.88 (+/-0.53)mg-min/L in these cultures. Increase in growth temperature from 22.5 degrees C to 35 degrees C for unamended 2NB cultures resulted in a 42-fold decrease in C*T(99.9) values for chlorine. A similar change in temperature resulted in no significant change in C*T(99.9) values for chloramine. These results indicate that inactivation of K. pneumoniae cultures by chlorine was highly sensitive to changes in growth conditions unlike inactivation by chloramine.     

Size effect in reactivity of copper nanoparticles to carbon tetrachloride degradation

Surface area-normalized rate constants (k(SA)) of reaction between metallic nanoparticles and reducible contaminants, such as chlorinated hydrocarbons, heavy metals, and nitrate, have been reported to be dramatically increased as compared to that of commercial metallic powder. However, k(SA) for individual pollutants in previously published data vary by as much as 1-2 orders of magnitude and much of this variability is due to the effect of various sizes. The size dependence of the reactivity of nanoparticles is not yet fully understood; however, yielding nanoparticles with uniform size and without agglomeration during the period of reaction would demonstrate the effect of varying particle size. In this study, resin-supported zerovalent copper with average particle size of 7, 10, 18, 26, and 29, respectively, were successfully synthesized and evidenced no agglomeration during the reaction period of 10h. The k(SA) of copper nanoparticles (k(n,SA)) was 110-120 times higher than that of powdered copper particles (k(p,SA)) when the copper particle size was about 10nm. However, for diameters of 18-29 nm, the ratio of k(n,SA)/k(p,SA) was around 10-20, indicating that the reactivity of small copper nanoparticles (approximately 10nm) varies discontinuously. Thus, most variability in previous k(SA) is attributed to the presence of small nanoparticles.     

Electrocatalytic reduction of nitrate in water

Nitrate (NO(3)(-)) contamination of groundwater is a common problem throughout intensive agricultural areas (nonpoint source pollution). Current processes (e.g., ion exchange, membrane separation) for NO(3)(-) removal have various disadvantages. The objective of this study was to evaluate an electrocatalytic reduction process to selectively remove NO(3)(-) from groundwater associated with small agricultural communities. A commercially available ELAT (E-Tek Inc., Natick, MA) carbon cloth with a 30% surface coated Rh (rhodium) (1microg x cm(-1)) was tested at an applied potential of -1.5 V versus standard calomel electrode (SCE) with a Pt auxiliary electrode. Electrocatalytic reduction process (electrolysis) of NO(3)(-) was tested with cyclic voltammetry (CV) in samples containing NO(3)(-) and 0.1M NaClO(4)(-). Nitrate and NO(2)(-) concentrations in test solutions and groundwater samples were analyzed by ion chromatography (IC). The presence of Rh on the carbon cloth surface resulted in current increase of 36% over uncoated carbon cloths. The electrocatalysis experiments using Rh coated carbon cloth resulted in reduction of NO(3)(-) and NO(2)(-) on a timescale of minutes. Nitrite is produced as a product, but is rapidly consumed upon further electrolysis. Field groundwater samples subjected to electrocatalysis experiments, without the addition of NaClO(4)(-) electrolyte, also exhibited removal of NO(3)(-) on a timescale of minutes. Overall, results suggest that at an applied potential of -1.5 V with respect to SCE, Rh coated carbon cloth can reduce NO(3)(-) concentrations in field groundwater samples from 73 to 39 mg/L (16.58 to 8.82 mg/L as N) on a timescale range of 40-60 min. The electrocatalytic reduction process described in this study may prove useful for removing NO(3)(-) and NO(2)(-) from groundwater associated with nonpoint source pollution.     

Formulation of a mathematical model to predict solar water disinfection

A mathematical model was formulated that will facilitate the prediction of solar disinfection by analyzing the effect of sunlight exposure (x(1)) and the load of bacterial contamination (x(2)), as predictor variables, on the efficiency of solar disinfection (y). Aliquots of 0.1 ml containing average numbers of E. coli, ranging between 1 and 5 x 10(3)cells/ml raw water, were introduced into each of the 96 wells of polystyrene microtitre plates. Plates, with the lid on, were exposed to sunlight for varying exposures ranging between 1.04 x 10(3) and 8.40 x 10(3)kJ m(-2). Double strength nutrient broth was then added. After 48 h incubation wells containing visible contamination were considered as containing one cell or more that survived the exposure. Data showed that disinfection is dependent both on the load of bacterial contamination and sunlight exposure. This relationship is characterized by curves having shoulders followed by a steep decline and then tailing off in an asymptotic fashion. The shoulder size increased with the increase of the contamination load, however, the slope remains the same. Statistical analysis indicates a positive correlation among the variables (R(2) = 0.893); the mathematical model, y=1-(1-e(-kx(1)))(x(2)), represents the relationship, with k being the solar inactivation constant. The exposure required to produce a given decontamination level can be predicted using the equation: x(1)=-1/kln[1-(1-y)(-1/x(2))]e(-micro/rho.m/A), where micro is the linear attenuation coefficient (m(-1)), rho is the density, m is the mass and A is the area of the exposed part of the sample. The predictor variables (x(1), x(2)) strongly influence the efficiency of solar disinfection, which can be predicted using the suggested mathematical model. The present data provides a means to predict the efficiency of solar disinfection as an approach to improve the quality of drinking water mainly in developing countries with adequate sunshine all year-round.     

Complexation of organic compounds in the presence of Al3+ during micellar flocculation

Complexes of Al and model pollutants phenol, benzoic acid, 2,4-D (2,4-dichlorophenoxyacetic acid) and 2,4-DB (2,4-dichlorophenoxybutiric acid) play a key role in the removal of organic pollutants by co-adsorption on micelles of anionic surfactants flocculated by means of Al(3+). This technique, known as adsorptive micellar flocculation (AMF), is related to removal of organic compounds by coagulation-precipitation with Al and Fe salts. Some of the stoichiometries found (6Al:1L and higher, with "L" the organic compound) indicate that complexes of a cationic nature form in the presence of high excesses of Al, possibly polyaluminium complexes related to the species [Al(13)O(4)(OH)(24)](7+). In the case of phenol it has been established by spectroscopic measures that in the range of [Al(2)(SO(4))(3)](tot) between 5 x 10(-5) and 3 x 10(-4)M and [phenol](tot) between 10(-3) and 6 x 10(-3)M complexes exist at pH as low as 2.4. The results show that AMF may be explained by the chemisorption of molecules of organic compounds able to incorporate into the polyaluminic complexes occurring within the Stern layer of flocculating micelles.     

Fenton oxidation of cork cooking wastewater--overall kinetic analysis

In the present work, the possibility of using chemical oxidation through Fenton's reagent for the pre-treatment of cork cooking wastewaters was exploited. Aiming both the selection of the best operating conditions (pH, Fe2+:H2O2 ratio and initial H2O2 concentration) and the evaluation of the overall reaction kinetics, trials were performed in a batch reactor. Operating at pH = 3.2, H2O2 concentration = 10.6 g/L and Fe2+:H2O2 ratio = 1:5 (by weight), about 66.4% of total organic carbon (TOC), 87.3% of chemical oxygen demand (COD) and 70.2% of biochemical oxygen demand (BOD5) were removed and an increase of the BOD5/COD ratio from 0.27 to 0.63 was achieved. In the temperature range 20-50 degrees C, the best performance was obtained at 30 degrees C. The kinetic study was undertaken at different initial TOC concentrations and temperatures. Overall kinetics can be described by a second-order followed by a zero-order rate equation and the apparent kinetic constants at 30 degrees C are k = 2.3 x 10(-4) L/mg min and k0 = 26.0 mg/L min, respectively. The experiments performed at different temperatures confirmed the global kinetic model and allowed to calculate the global activation energy for the second-order reaction (70.7 kJ/mol).     

Photodegradation of DDT with the photodeposited ferric ion on the TiO2 film

The photodegradation capability of DDT has been enhanced by Fe/TiO2 film in a photoreactor with UV radiation. The optimal thickness of TiO2 for the DDT photodegradation was 2.94 microm with a 3-time coating, where the first-order rate constant was 0.077 min(-1). The optimal Fe3+(ferric ion) photodeposition amount was estimated as 3.7 x 10(-4) mg mm(-2) corresponding with 0.73 mg Fe3+ (mg TiO2)(-1). Photoremoval rate of DDT increased with an increasing pH value, while the pH value of solution decreased to acidic region during the DDT photodegradation. The photodegradation efficiency was 85% in 20 min with only TiO2 film and increased from 85% up to 96% by the photodeposition of 0.73 mg Fe3+ (mg TiO2)(-1) on TiO2 film as a sensitizer since the band gap energy of Fe2O3 (2.2 eV) is lower than that of TiO2 (3.0 eV).     

黄河口表层沉积物中的可提取铜和锌

通过偏相关分析和逐步回归分析发现黄河口及其附近海域表层沉积物中可提取铜主要结合在水含氧化物和粘土矿的外表面上．而可提取锌主要结合在水合氧化铁上，其次结合在水含氧化锰上．用１ｍｏｌ盐酸提取沉积物中的铜、锌、铁和锰，同时测定了沉积物的外比表面积．     

Removal of 1,4-dioxane from water using sonication: effect of adding oxidants on the degradation kinetics

This research investigates the effect of adding oxidants such as Fe0, Fe2+ and S2O8(2-) in the sonication of 1,4-dioxane (1,4-D). The results indicate that the degradation pattern of 1,4-D kinetically could be divided into three steps (initiation, acceleration, and stabilization), with the first two steps predominating. The initiation step agreed with zero order rate model, while the acceleration step was the pseudo-first order. In the presence of HCO3- as a radical scavenger, the degradations of 1,4-D and TOC were suppressed, indicating that OH radical is an important factor in the sonolysis, especially at the acceleration step. The overall degradation efficiency of 79.0% in the sonolysis of 1,4-D was achieved within 200 min. While Fe0, Fe2+ and S2O8(2-) were individually combined with sonication, the total degradation efficiency of 1,4-D increased 18.6%, 19.1% and 16.5% after 200 min, respectively. The addition of oxidants not only increased the rate constant in the acceleration step, but also changed the kinetic model from zero to pseudo-first order at the initiation step. The addition of oxidants such as Fe2+, Fe0 and S2O8(2-) in the sonication of 1,4-D also improved the mineralization of 1,4-D. However, the degradation efficiencies of 1,4-D and TOC were not statistically different (p = 0.709, ANOVA) with different oxidants such as Fe2+, Fe0 and S2O8(2-).     

Oxidative degradation of N-nitrosodimethylamine by conventional ozonation and the advanced oxidation process ozone/hydrogen peroxide

This study investigates the oxidative degradation of N-nitrosodimethylamine (NDMA), a probable human carcinogen, by conventional ozonation and the advanced oxidation process ozone/hydrogen peroxide (AOP O(3)/H(2)O(2)). The rate constants of reactions of NDMA with ozone and hydroxyl radical ((*)OH) were determined to be 0.052+/-0.0016M(-1)s(-1) and (4.5+/-0.21)x10(8)M(-1)s(-1), respectively. The experiments performed with buffered deionized water varying solution pH and employing H(2)O(2) and HCO(3)(-) clearly showed that the reaction with (*)OH dominates the NDMA oxidation during ozonation. Conventional ozonation with up to 160 microM (=7.7 mgL(-1)) ozone led to less than 25% NDMA oxidation in natural waters. The AOP O(3)/H(2)O(2) required 160-320 microM ozone ([O(3)](0)/[H(2)O(2)](0)=2:1) to achieve 50-75% NDMA oxidation. However, multiple injections of ozone of the same overall dose somewhat improved the oxidant utilization efficiency by minimizing (*)OH scavenging contribution of oxidants. Methylamine (MA) was found to be a major amino product from NDMA oxidation initiated by (*)OH. The mechanism of NDMA oxidation to MA is discussed based on the results obtained in this study and the previous literature. Bromate formation may be the limiting factor for NDMA oxidation during ozonation and ozone-based AOPs in bromide-containing waters.     

Applicability of alkaline hydrolysis for remediation of TNT-contaminated water

This study was conducted to assess the applicability of alkaline hydrolysis as an alternative ex situ technology for remediating 2,4,6-trinitrotoluene (TNT)-contaminated water. TNT reactivity had a strong dependence on the reaction pH (11-12) and initial TNT (5-25 mg L(-1)) in batch systems, resulting in pseudo first-order transformation rate, k ranging between 1.9 x 10(-3) and 9.3 x 10(-5) min(-1). In continuous flow stirred-tank reactor (CFSTR) systems with initial TNT of 1 mg L(-1), the highest 74% of TNT reduction was achieved at the reaction pH of 11.9 and 2-day hydraulic retention time under steady-state condition. Oxalate was produced as the major hydrolysate in the CFSTRs, indicating a ring cleavage during alkaline hydrolysis. It was also believed that TNT alkaline hydrolysis occurred through the production of color-forming intermediates via dimerization. It is concluded that alkaline hydrolysis can be an alternative treatment technology for remediation of TNT-contaminated water.