Bromine addition and successive amine substitution of mesoporous ethylenesilica: Reaction, characterizations and arsenate adsorption

Bromination and subsequent ethylenediamine substitution of the CC double bond in mesoporous ethylenesilica were carried out to explore the characteristics of this periodic mesoporous organosilica. The structures of the products (BrPMO and EDA–BrPMO, respectively) were analysed by IR, Br K-edge EXAFS and NMR spectroscopies, as well as X-ray diffraction and nitrogen adsorption. We showed (1) that the formulae of the two products that formed were [CHBrSiO_1.5]_0.45[CHSiO_1.5]_0.55 and [NH₂CH₂CH₂NHCHSiO_1.5]_0.05 [CHBrSiO_1.5]_0.40[CHSiO_1.5]_0.55, respectively, (2) that the addition of Br₂ at room temperature occurred on the CC double bonds with disturbing the framework structure, (3) that IR absorption band of CC bonds that reacted with Br₂ is significantly different from that of inactive CC bond, (4) that the length of the C–Br bond was considerably longer than in conventional alkyl bromides, and (5) that a large proportion of the ν(C–Br) band remained at the same position in the IR absorption spectrum after the ethylenediamine (EDA) substitution, while a new ν(C–Br) absorption also appeared. The mechanisms of these reactions are discussed at both the micro and mesoscopic levels.

Arsenate adsorption on EDA–BrPMO, in which the EDA is directly bound to the “surface” of the mesopores, was compared with adsorption on EDA–Pr–PMO, which was prepared by the direct synthesis of 3-chloropropyl-functionalized mesoporous ethanesilica followed by the substitution of Cl with EDA. The strength of the adsorption, as measured with the distribution coefficient, was greater for the former adsorbent than the latter. The origin of this difference was attributed to the distance between amino group and the surface.     

Kinetics,equilibrium and thermodynamics studies of arsenate adsorption from aqueous solutions onto iron hydroxide

This paper reports the equilibrium, kinetics and thermodynamic studies of arsenate adsorption onto freshly precipitated iron hydroxide. Adsorption of arsenate onto iron hydroxide depends on arsenate concentration, contact time and temperature. The intrapartical diffusion model indicates that both the film and intrapartical diffusion control arsenate adsorption on iron hydroxide. The values of activation energies (E_a) indicate the chemical nature of adsorption accompanied by diffusion controlled processes as the rate limiting step. The endothermic nature of the adsorption process suggests that adsorption reaction consumes energy. The negative values of ΔS^# can be assigned to decreased randomness at the solid liquid interface.     

Arsenic uptake potential of water lettuce (Pistia Stratiotes L.)

Arsenate uptake by aquatic plant water lettuce (Pistia stratiotes L.) was studied in the laboratory condition to investigate a low cost natural aquatic treatment system for pollutant removal. The plants were harvested from a local pollution‐free pond in young condition and hydroponically cultured in the laboratory. Bio‐accumulation was noticed to be both concentration and duration dependent. The results show that the plant could effectively absorb arsenic between a range of 0.25 to 5.0 mg/l to the extent of 82.0 to 22.8% for a biomass of 20 g/l at pH 7.0 after 144 h. The results were also plotted in Langmuir and Freundlich isotherms and the data were well fitted. The sorption capacity was evaluated as 1.43 mg/g for the Langmuir isotherm and 1.01 mg/g for the Freundlich isotherm. The removal efficiency was, however, noted to be maximum (87.5%) at pH 6.5. The effect of biomass quantity has also been investigated along with some metabolic parameters.     

Retention of inorganic arsenic by coryneform mutant strains

The natural resistance mechanisms of corynebacteria to respond to the environments containing high levels of arsenic were successfully adopted to develop inexpensive and selective extractants for submicrogram amounts of arsenic. Kinetic and equilibrium characteristics were evaluated, and a preliminary exploration of the capability of these strains to be used for arsenic speciation was also made in this work. Three kinetics models were used to fit the experimental data. It was found that the pseudo-first-order kinetics model was not quite adequate to describe the retention process, while the intraparticle diffusion and the pseudo-second-order kinetics models provide the best fits. The equilibrium isotherm showed that the retention of arsenic was consistent with the Langmuir equation and that the Freundlich and Dubinin-Radushkevich models provided poorer fits to the experimental data. The maximum effective retention capacity for arsenic was about 15.4 ng As/mg biomass. The amount of arsenic retained was directly measured in the biomass by forward planning a slurry electrothermal atomic absorption spectrometric procedure.     

Efficient removal of chromate and arsenate from individual and mixed system by malachite nanoparticles

Malachite nanoparticles of 100-150 nm have been efficiently and for the first time used as an adsorbent for the removal of toxic arsenate and chromate. We report a high adsorption capacity for chromate and arsenate on malachite nanoparticle from both individual and mixed solution in pH ～4-5. However, the adsorption efficiency decreases with the increase of solution pH. Batch studies revealed that initial pH, temperature, malachite nanoparticles dose and initial concentration of chromate and arsenate were important parameters for the adsorption process. Thermodynamic analysis showed that adsorption of chromate and arsenate on malachite nanoparticles is endothermic and spontaneous. The adsorption of these anions has also been investigated quantitatively with the help of adsorption kinetics, isotherm, and selectivity coefficient (K) analysis. The adsorption data for both chromate and arsenate were fitted well in Langmuir isotherm and preferentially followed the second order kinetics. The binding affinity of chromate is found to be slightly higher than arsenate in a competitive adsorption process which leads to the comparatively higher adsorption of chromate on malachite nanoparticles surface.     

Dissolved organic matter and arsenic removal with coupled chitosan/UF operation

Long time uptake arsenic will cause cancers and blackfoot disease. There are still several million people suffering from drinking arsenic contaminated water. This work studied the performance of coupled chitosan/UF for arsenic removal and the influence of dissolved organic matter on arsenic removal with UF operation. Humic acid representing dissolved organic matter was fractionated into five groups of molecular sizes by gel filtration chromatography. Arsenic rejection by UF under the experimental condition is only 10%. In the presence of humic compounds, the arsenic removal of 22% is obtained. DOM with apparent molecular weight > 35,000 Da is the principle component responsible for chelating arsenic and thereafter being rejected by UF membrane. The combined interactions of humic compounds, chitosan, and arsenic enable a 65% arsenic rejection by UF. The results presented here enable our understanding of the complicated mechanisms involved in chitosan/UF/DOM/arsenic system.     

Adsorption of As(V) from Water Using Nanomagnetite

This paper describes a study of the removal of arsenate [As(V)] from aqueous solutions by adsorption on commercial nanomagnetite (NM). The influences of pH, initial arsenate [As(V)] concentration, and adsorbent concentration were investigated in multiple kinetic runs. The adsorption kinetics and isotherms were investigated in batch experiments. The experimental data were determined to be best described by the pseudosecond-order kinetic model. Langmuir and Freundlich isotherms were used to fit the adsorption data from equilibrium experiments. The findings have revealed that NM has high removal efficiency for arsenate, with its capacity to reduce an initial level of 300 to <5-μg/L As(V), i.e., below the limit (10-μg/L As) set for potable water by the World Health Organization.     

Urinary arsenic methylation capability and carotid atherosclerosis risk in subjects living in arsenicosis-hyperendemic areas in southwestern Taiwan

Long-term exposure to inorganic arsenic from artesian drinking well water is associated with carotid atherosclerosis in the Blackfoot Disease (BFD)-hyperendemic area in Taiwan. The current study examined the arsenic methylation capacity and its risk on carotid atherosclerosis. A total of 304 adults (158 men and 146 women) residing in the BFD-hyperendemic area were included. The extent of carotid atherosclerosis was assessed by duplex ultrasonography. Chronic arsenic exposure was estimated by an index of cumulative arsenic exposure (CAE) and the duration of artesian well water consumption. Urinary levels of inorganic arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid [MMA(V)] and dimethylarsinic acid [DMA(V)] were determined by high performance liquid chromatography linked on-line to a hydride generator and atomic absorption spectrometry (HPLC-HG-AAS). The percentage of arsenic species, primary methylation index [PMI = MMA(V) / (As(III) + As(V)] and secondary methylation index [SMI = DMA(V) / MMA(V)] were calculated and employed as indicators of arsenic methylation capacity. Results showed that women and younger subjects had a more efficient arsenic methylation capacity than did men and the elderly. Carotid atherosclerosis cases had a significantly greater percentage of MMA(V) [%MMA(V)] and a lower percentage of DMA [%DMA (V)] compared to controls. Subjects in the highest two tertiles of PMI with a median of CAE > 0 mg/L-year had an odds ratio (OR) and a 95% confidence interval (CI) of carotid atherosclerosis of 2.61 and 0.98-6.90 compared to those in the highest two tertiles of PMI with a CAE = 0 mg/L-year. We conclude that individuals with greater exposure to arsenic and lower capacity to methylate inorganic arsenic may be at a higher risk to carotid atherosclerosis.     

利用纳米材料吸附去除饮用水中砷(Ⅴ)的研究

研究纳米材料对人工配水中砷(Ⅴ)吸附去除的规律和影响因素,为研制新型除砷材料提供一定的理论依据。分别选取不同的纳米材料和常规除砷材料,利用静态试验对人工配水中砷(Ⅴ)进行去除效果的比较,并探讨环境因素对去除效果的影响。结果表明纳米材料的除砷效果优于常规除砷材料,试验中纳米ZnO的除砷效果较好,接触0.5 h后去除率即可达到99.9%,去除效果受温度、pH和常见阴离子Cl-、SO24-影响小。纳米ZnO对水中砷(Ⅴ)的去除效果较好,经过进一步的研究有望应用于饮水除砷(Ⅴ)。     

Arsenate removal from water using sand--red mud columns

This study describes experiments in which sorption filters, filled with chemically modified red mud (Bauxsol) or activated Bauxsol (AB) coated sand, are used to remove As(V) (arsenate) from water. Bauxsol-coated sand (BCS) and AB-coated sand (ABCS) are prepared by mixing Bauxsol or AB with wet sand and drying. Samples of the BCS and ABCS are also used in batch experiments to obtain isotherm data. The observed adsorption data fit the Langmuir model well, with adsorption maxima of 3.32 and 1.64 mgg(-1) at pH values of 4.5 and 7.1, respectively for BCS; and of 2.14 mgg(-1) for ABCS at a pH of 7.1. Test results show that higher arsenate adsorption capacities can be achieved for both BCS and ABCS when using the columns compared to results for batch experiments; the difference is greater for BCS. Additional batch tests, carried out for 21 days using BCS to explain the observed discrepancy, show that the equilibrium time previously used in batch experiments was too short because adsorption continued for at least 21 days and reached 87% after 21 days compared to only 35% obtained after 4h. Fixed bed column tests, used to investigate the effects of flow rate and initial arsenate concentration indicate that the process is sensitive to both parameters, with lower flow rates (longer effective residence times in the columns) and initial arsenate concentrations providing better column performance. An examination of the combined effect of potential competing anions (i.e. silicate, phosphate, sulphate and bicarbonate) on the column performance showed that the presence of these anions in tap water slightly decreases arsenate removal. Each breakthrough curve is compared to the Thomas model, and it is found that the model may be applied to estimate the arsenate sorption capacity in columns filled with BCS and ABCS. The data obtained from both batch and column studies indicate that BCS and ABCS filtration could be effectively used to remove arsenate from water, with the latter being more efficient.