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1.
Worldwide, arsenic contamination has become a matter of extreme importance owing to its potential toxic, carcinogenic and mutagenic impact on human health and the environment. The magnetite-loaded biochar has received increasing attention for the removal of arsenic (As) in contaminated water and soil. The present study reports a facile synthesis, characterization and adsorption characteristics of a novel magnetite impregnated nitrogen-doped hybrid biochar (N/Fe3O4@BC) for efficient arsenate, As(V) and arsenite, As(III) removal from aqueous environment. The as-synthesized material (N/Fe3O4@BC) characterization via XRD, BET, FTIR, SEM/EDS clearly revealed magnetite (Fe3O4) impregnation onto biochar matrix. Furthermore, the adsorbent (N/Fe3O4@BC) selectivity results showed that such a combination plays an important role in targeted molecule removal from aqueous environments and compensates for the reduced surface area. The maximum monolayer adsorption (Qmax) of developed adsorbent (N/Fe3O4@BC) (18.15 mg/g and 9.87 mg/g) was significantly higher than that of pristine biochar (BC) (9.89 & 8.12 mg/g) and magnetite nano-particles (MNPs) [7.38 & 8.56 mg/g] for both As(III) and As(V), respectively. Isotherm and kinetic data were well fitted by Langmuir (R2 = 0.993) and Pseudo first order model (R2 = 0.992) thereby indicating physico-chemical sorption as a rate-limiting step. The co-anions (PO43-) effect was more significant for both As(III) and As (V) removal owing to similar outer electronic structure. Mechanistic insights (pH and FTIR spectra) further demonstrated the remarkable contribution of surface groups (OH, –NH2 and –COOH), electrostatic attraction (via H- bonds), surface complexation and ion exchange followed by external mass transfer diffusion and As(III) oxidation into As(V) by (N/Fe3O4@BC) reactive oxygen species. Moreover, successful desorption was achieved at varying rates up to 7th regeneration cycle thereby showing (N/Fe3O4@BC) potential practical application. Thus, this work provides a novel insight for the fabrication of novel magnetic biochar for As removal from contaminated water in natural, engineering and environmental settings.  相似文献   

2.
The present work demonstrates the utility of polymer embedded nanocrystalline titania (TiP) as a new, accessible and viable solid sorbent for the chromatographic separation of high specific activity 77As from neutron irradiated natural GeO2. Experimental parameters such as distribution ratios (K d), equilibrium sorption capacity, breakthrough capacity and separation yields were determined. A two-step ion-exchange procedure was developed to avail 77As, from irradiated Ge in alkaline medium. The first step involved removal of the bulk Ge from 77As by selective sorption of Ge ions on a TiP column at pH 13. Subsequently, the effluent solution containing 77As was further purified and concentrated by sorption on a small TiP column at pH 10. 77As could be eluted from the second column in 2?C3?mL of 0.1?M NaOH solution with >80% radiochemical yield. The 77As obtained by this method was found to have insignificantly small level of radiocontaminants.  相似文献   

3.
A novel adsorbent of multi-wall carbon nanotubes (MWCNTs) chemically modified silica (MWCNTs-silica) was synthesised and employed as the adsorbent material for solid-phase extraction (SPE) of trace Zn(II), Cu(II), Cd(II), Cr(III), V(V) and As(V) in environmental water samples followed by inductively coupled plasma optical emission spectrometry detection. This material inherits the advantages of nanomaterial MWCNTs and conventional silica with dual functional groups (–NH2 and –COOH), and avoid the problem of nanomaterial in SPE, such as high pressure. The factors affecting the separation and preconcentration of target elements such as pH, sample flow rate and volume, eluent concentration and volume were investigated. Under the optimised conditions, the detection limits for Zn(II), Cu(II), Cd(II), Cr(III), V(V) and As(V) were 0.27, 0.11, 0.45, 0.91, 0.55 and 0.67 μg L?1 with the relative standard deviations of 3.1, 5.9, 4.1, 4.0, 7.3 and 8.6% (c = 10 μg L?1, n = 7), respectively. The adsorption capacity of MWCNTs-silica was 26.6, 70.0, 13.8, 58.0, 20.0 and 20.0 mg g?1 for Zn(II), Cu(II), Cd(II), Cr(III), V(V) and As(V), respectively, and the prepared adsorbent could be reused more than 100 times. In order to validate the developed method, two certified reference materials of GSBZ50009-88 and GSBZ 50029-94 environmental waters were analysed and the determined values were in good agreement with the certified values. The developed method has been applied to the determination of trace elements in environmental water samples with satisfactory results.  相似文献   

4.
李勋  汪正浩 《中国化学》2007,25(3):295-299
A new direct procedure for the determination of inorganic arsenic species was developed by electrochemical hydride generation atomic absorption spectrometry (EcHG-AAS) with selective electrochemical reduction. The determination of inorganic arsenic species is based on the fact that As(Ⅲ) shows significantly higher absorbance at low electrolytic currents than As(Ⅴ) in 0.3 mol·L^-1 H2SO4. The electrolytic current used for the determination of As(Ⅲ) without considerable interferences of As(Ⅴ) was 0.4 A, whereas the current for the determination of As(Ⅲ) and As(Ⅴ) was 1.2 A. For equal concentrations of As(Ⅲ) and As(Ⅴ) in a sample, the interferences of As(Ⅴ) during the As(Ⅲ) determination were smaller than 5%. The absorbance for As(Ⅴ) could be calculated by subtracting that for As(Ⅲ) measured at 0.4 A from the total absorbance for As(Ⅲ) and As(Ⅴ) measured at 1.2 A, and then the concentration of As(Ⅴ) can be obtained by its calibration curve at 1.2 A. The methodology developed provided the detection limits of 0.3 and 0.6 ng·mL^-1 for As(Ⅲ) and As(Ⅴ), respectively. The relative standard deviations were of 3.5% for 20 ng·mL^-1 As(Ⅲ) and 3.2% for 20 ng·mL^-1 As(Ⅴ). The method was successfully applied to determination of soluble inorganic arsenic species in Chinese medicine.  相似文献   

5.
A simple method was developed for separation of bromine from metallic selenium. This method enables easy preparation of77Br by proton bombardment of metallic selenium (enriched77Se or78Se). The method consists of heating the metallic selenium with H2O to 300°C in a small autoclave for about three hours. The77Br is distilled from the obtained solution after the addition of H2SO4+K2Cr2O7. The step also removes the arsenic produced together with the selenium.  相似文献   

6.
Ferric nitrate–graphene (FG) nanocomposites synthesized via the equivalent‐volume impregnation method were used for the removal of As(V) species from simulated arsenic‐containing wastewater. Effects of various factors were assessed, such as the reaction temperature, solution pH, adsorbent dosage, and reaction time. The results indicated that the As(V) removal efficiency was as high as 99%, and the concentration of arsenic‐containing wastewater after FG treatment was as low as 9.4 μg L–1 as a result of the optimal absorption capacity and maximum specific surface area (171.766 m2/g) of this material. The equilibrium adsorption capacity of FG for As(V) was achieved in approximately 20 min, and the maximum adsorption capacity was calculated to be 112.4 mg g–1 by Langmuir adsorption isotherm, which was higher than that of other adsorbents such as manganese‐incorporated iron(III) oxide–graphene (14.42 mg g–1). Moreover, the removal efficiency of As(V) can be maintained above 95% under acidic and alkaline conditions. Brunauer–Emmett–Teller analysis showed that the modified FG pore structure was regular. Based on the characterizations by X‐ray diffraction, X‐ray photoelectron spectroscopy, and Fourier transform infrared, the products on the surface of the used FG were Fe(OH)3, FeAsO4, and other compounds, and As(V) was mainly removed by the formation of insoluble compounds and coprecipitation.  相似文献   

7.
This paper describes a new voltammetric procedure for the inorganic speciation of As(III) and As(V) in water samples. The procedure is based on the chemical reduction of arsenate [As(V)] to arsenite [As(III)] followed by the voltammetric determination of total arsenic as As(III) at the hanging mercury drop electrode (HMDE) by adsorptive cathodic stripping voltammetry (AdCSV) in the presence of sodium diethyl dithiocarbamate (SDDC). The reduction step involved the reaction with a mixture of Na2S2O5 and Na2S2O3 in the concentrations 2.5 and 0.5 mg mL?1, respectively, and the sample heating at 80 °C for 45 min. The linear range for the determination of total arsenic as As(III) in the presence of SDDC was between 5 and 150 μg L?1 for a deposition time of 60 s (r=0.992). A detection limit of 1.05 μg L?1 for total As was calculated for the method in water samples using a deposition time of 60 s. The detection limits of 4.2 μg L?1 and 15.0 μg L?1 for total As in seawater and dialysis concentrates, respectively, were calculated using a deposition time of 60 s. The relative standard deviations calculated were 2.5 and 4.0% for five measurements of 20 μg L?1 As(V) as As(III) in water and dialysis concentrates, respectively, after chemical reduction under optimized conditions. The method was applied for the determination of As(III) and total As in samples of dialysis water, mineral water, seawater and dialysis concentrates. Recovery values between 86.0 and 104.0% for As(III) and As(V) added to the samples prove the satisfactory accuracy and applicability of the procedure for the arsenic monitoring.  相似文献   

8.
Arsenic compounds including arsenous acid (As(III)), arsenic acid (As(V)), dimethylarsinic acid (DMA) and monomethylarsonic acid (MMA) were separated by high-performance liquid chromatography (HPLC) and detected by inductively coupled plasma mass spectrometry (ICP-MS). A Hamilton PRX-100 anionic-exchange column and a pH 8.5 K2HPO4/KH2PO4 5.0 × 10−3 mol L−1 mobile phase were used to achieve arsenic speciation. The separation of arsenic species provided peaks of As(III) at 2.75 min, DMA at 3.33 min, MMA at 5.17 min and As(V) at 12.5 min. The detection limits, defined as three times the standard deviation of the lowest standard measurements, were found to be 0.2, 0.2, 0.3 and 0.5 ng mL−1 for As(III), DMA, MMA and As(V), respectively. The relative standard deviation values for a solution containing 5.0 μg L−1 of As(III), DMA, MMA and As(V) were 1.2, 2.1, 2.5 and 3.0%, respectively. This analytical procedure was applied to the speciation of arsenic compounds in drinking (soft drink, beer, juice) samples. The validation of the procedure was achieved through the analysis of arsenic compounds in water and sediment certified reference materials.  相似文献   

9.
An improved method for production of >100 mCi of77Br with the78Se(p, 2n)77Br nuclear reaction and a 4π water-cooled target containing encapsulated metallic78Se or a Pb78Se alloy has been developed. The77Br was separated with ∼98% radiochemical yield and a radionuclidic purity of 98.9%. The time required to isolate carrier-free77Br free of metallic impurities was less than 4hrs. Isotopically enriched78Se was quantitatively recovered. This research was partially supported by NIH Grant No. Ro1 H1 18487-01, and Performed at Brookhaven National Laboratory under contract with the U.S. Department of Energy and supported by its Division of Basic Energy Sciences.  相似文献   

10.
In this work, dual‐column capillary microextraction (CME) system consisting of N‐(2‐aminoethyl)‐3‐aminopropyltrimethoxysilane (AAPTS)‐silica coated capillary (C1) and 3‐mercaptopropyl trimethoxysilane (MPTS)‐silica coated capillary (C2) was developed for sequential separation/preconcentration of arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid [MMA(V)] and dimethylarsinic acid [DMA(V)] in the extracts of human hair followed by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV‐ICP‐MS) detection with iridium as permanent modifier. Various experimental parameters affecting the dual‐column microextraction of different As species had been investigated in detail. It was found that at pH 9, As(V) and MMA could be quantitatively retained by C1 and only As(III) could be quantitatively retained by C2. With the aid of valve switching, As(V)/MMA(V) retained on C1 and As(III) retained on C2 could be sequentially desorbed by 10 µl of 0.01 mol l?1 HNO3 [for As(V)], 0.1 mol l?1 HNO3 [for MMA(V)] and 0.2 mol l?1 HNO3‐3% thiourea (m/v) [for As(III)], respectively, the eluents were immediately introduced into the Ir‐coated graphite tubes for further ETV‐ICP‐MS detection. With two‐step ETV pyrolysis program, Cl? in the sample matrix could be in situ removed, and the total As in the human hair extracts or digested solution could be interference‐free, determined by ETV‐ICP‐MS. DMA(V) in the human hair extracts was obtained by subtraction of total As in the human hair extracts from other three As species. Under the optimized conditions, the detection limits (3 σ) of the method were 3.9 pg ml?1 for As(III), 2.7 pg ml?1 for As(V), 2.6 pg ml?1 for MMA(V) and 124 pg ml?1 for total As with the relative standard deviations less than 7.0% (C = 0.1 ng ml?1, n = 7), and the enrichment factor was 286, 262 and 260 for As(III), As(V) and MMA(V), respectively. The developed method was successfully applied for the speciation of arsenic in the extracts of human hair. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

11.
A new method was developed for the speciation of inorganic arsenic in environmental water by using selective magnetic solid-phase extraction followed by inductively coupled plasma mass spectrometry. It is found that As(V) selectively adsorbed on amino-modified silica-coated magnetic nanoparticles (MNPs) in the pH range from 3 to 8, while As(III) is not be retained. The As(V)-loaded MNPs can be separated easily from the aqueous sample solution by simply applying an external magnetic field. The adsorbed As(V) was quantitatively recovered from the MNPs using using 1 M nitric acid. Total inorganic As was extracted after the permanganate oxidation of As(III) to As(V). Parameters affecting the separation were investigated systematically, and the optimal separation conditions were established. Under the optimal conditions, the limit of detection is 0.21 ng L?1, and the precision is 6.8% (at 10 ng L?1, for n?=?7). The method was applied to the speciation of inorganic arsenic in environmental water of tobacco growing area.
Figure
A new kind of silica-coated magnetic nanoparticles (SCMNPs) modified with AAPTS was synthesized and employed as magnetic solid phase extraction adsorbent for ICP-MS speciation of inorganicAs in environmental water  相似文献   

12.
A new chemiluminescence (CL) method for the selective determination of As(III) and As(V) ions in aqueous solution has been studied using a FIA system. The method is based on the increased CL intensity with the addition of As(V) ion into a solution of lucigenin and hydrogen peroxide. The addition of As(III) ion into the solution did not change the CL intensity. Total concentration of As ions was determined after pre-oxidation of As(III) to As(V) with hydrogen peroxide in basic solution. The As(III) content was estimated by subtracting the content of As(V) ion from total As concentration. The effects of concentrations of KOH and H2O2, and flow rates of reagents on CL intensity have been investigated. The calibration curve for As(V) ion was linear over the range from 1.0×10-2 to 10 μg/g, the coefficient of correlation was 0.997 and the detection limit was 5.0×10-3 μg/g under the optimal experimental conditions.  相似文献   

13.
To separate minor actinides from high level liquid waste (HLLW) of PUREX reprocessing, a silica-based macroporous isobutyl-BTP/SiO2-P adsorbent was synthesized by impregnating isobutyl-BTP (2,6-di(5,6-diisobutyl-1,2,4-triazin-3-yl)pyridine) extractant into the macroporous SiO2-P support with a mean diameter of 60 μm. A partitioning process using extraction chromatography for the treatment of HLLW was designed consisting five separation columns. As a partly work focused on isobutyl-BTP/SiO2-P separation column, adsorption behavior of 241Am and trivalent rare earth (RE) from simulated HLLW onto silica-based isobutyl-BTP/SiO2-P adsorbent was investigated by batch method. Meanwhile, the chemical and radiolytic stabilities of isobutyl-BTP/SiO2-P adsorbent against 0.01 M HNO3 solution and γ-ray irradiation were studied. It was found that isobutyl-BTP/SiO2-P adsorbent exhibited good adsorption selectivity for 241Am over RE(III) in 0.01 M HNO3 solution and showed weak or no adsorption affinity to light and middle RE(III) groups. In addition, in stability experiments, isobutyl-BTP adsorbent showed excellent stability against 0.01 M HNO3 solution and γ-ray irradiation over 4 months contact time.  相似文献   

14.
The potential of the Fe3O4, Mn3O4, and MnFe2O4 nanophases for the removal of arsenic(III) and (V) from aqueous solutions was investigated using the batch technique. The structure and grain size of the nanoadsorbents were characterized using XRD and Secherrer's equation. The Fe3O4, Mn3O4, and MnFe2O4 had the crystal structure of magnetite, hausmannite, and Jacobsite, while the grain sizes were 28, 25, and 12 nm, respectively. It was found that the sorption determined using 100 ppb of either As(III) or (V) was pH independent from pH 2 through pH 6. However, at pH below 3 the nanomaterials released high concentrations of iron and manganese into solution. The amount of both As(III) and (V) per gram of adsorbent was found to increase with increasing concentration of As in solution. The XRD analysis showed no decrease in the average grain size of the nanoadsorbents reacted with 1000 ppm of either As(III) or (V) or a combination of 500 ppm of each As species. Finally Fe3O4, Mn3O4, and MnFe2O4 showed binding capacities (µg/g) of 32.2, 8.9, and 718 for As(III) and 1575, 212 and 2125 for As(V), respectively.  相似文献   

15.
Novel shellfish waste-derived chitosan (CS) has been developed to adsorb As(V) from simulated wastewater under evaluating adsorption process parameters. The coexistence of some competing ions, like SiO32-, Cl-, NO3 and PO43- as well as the regeneration capacity of the spent adsorbent, was explored. The experimental data were modeled using several kinetics and isotherm models to understand the mechanism related to the uptake process. As(V) uptake was relatively rapid and highly dependent on pH. The Avrami-fractional-order expression supported data best, while the Liu equation described well isotherm data at pH 5.0. The maximum uptake capability (Liu) was 12.32 mg/g, and the highest removal performance (99 %) was obtained at optimum pH 5.0. Molecular dynamics simulations were performed to more clearly illuminate the atomic-level interactions between arsenic species and CS surface in both acidic and basic mediums. After four adsorption–desorption cycles, CS exhibited more than 90 % As(V) removal efficiency. The results of this study indicates that low cost shellfish derived chitosan is promising for efficient removal of As(V) from water body and can be used to remove other pollutants from watewater.  相似文献   

16.
An analytical procedure for determination of As(III) and As(V) in soils using sequential extraction combined with flow injection (FI) hydride generation atomic fluorescence spectrometry (HG-AFS) was presented. The soils were sequentially extracted by water, 0.6 mol l−1 KH2PO4 solution, 1% (v/v) HCl solution and 1% (w/v) NaOH solution. The arsenite (As(III)) in extract was analyzed by HG-AFS in the medium of 0.1 mol l−1 citric acid solution, then the total arsenic in extract was determined by HG-AFS using on-line reduction of arsenate with l-cysteine. The concentration of arsenate (As(V)) was calculated by the difference. The optimum conditions of extraction and determination were studied in detail. The detection limit (3σ) for As(III) and As(V) were 0.11 and 0.07 μg l−1, respectively. The relative standard deviation (R.S.D.) was 1.43% (n=11) at the 10 μg l−1 As level. The method was applied in the determination of As(III) and As(V) of real soils and the recoveries of As(III) and As(V) were in the range of 89.3-118 and 80.4-111%, respectively.  相似文献   

17.
Abstract

The title pseudo-arsonolipid with palmitoyl side chain has been prepared in ~70% yield from its parent DL-2,3-dihydroxybutane-1,4-bis(arsonic acid) after reduction of the As(V) to As(III) by thiophenol, acylation with palmitoyl chloride in the presence of pyridine and catalytic amounts of 4-(dimethylamino)pyridine, and reoxidation of As(III) to As(V) by hydrogen peroxide. In CDCl3/CD3OD esterification of the –AsO3H2 groups was detected by 1H NMR.  相似文献   

18.
Summary A sensitive HPLC method with marbofloxacin (MAR) as internal standard and fluorescence detection is described for the analysis of ofloxacin (OFL) enantiomers in plasma samples. Plasma samples were prepared by adding phosphate buffer (pH 7.4, 0.1m), then extracted with trichloromethane.S-OFL,R-OFL, and the internal standard were separated on a reversed-phase column with water-methanol, 85.5∶14.5, as mobile phase. The concentrations ofS-OFL andR-OFL eluting from the column (retention times 7.5 and 8.7 min, respectively) were monitored by fluorescence detection withλ ex = 331 andλ em = 488 nm. The detection and quantitation limits were 10 and 20 ng mL−1, respectively, forS-OFL and 11 and 21 ng mL−1 forR-OFL. Response was linearly related to concentration in the range 10 to 2500 ng mL−1. Recovery was close to 93% for both compounds. The method was applied to determination of the enantiomers of OFL in plasma samples collected during pharmacokinetic studies.  相似文献   

19.
Using as eluent a sequence of 3M HCl, 12M HCl, and 8M HNO3, a mixture of210Pb,210Bi, and210Po may be clearly separated on a column of Dowex 1×2−100 anion exchange resin. A Cherenkov count in H2O and the variation in count rate with time confirm that the nuclides emerge in the order210Pb→210Bi→210Po. If 12M HCl is replaced by 1.5M H2SO4/2.3 M Na2SO4, a clean separation also results, but recovery of210Po becomes considerably more difficult. All three nuclides are readily detectable by liquid scintillation counting, with the efficiency for210Pb in the 60–70% range. The Cherenkov aqueous counting efficiency for210Bi is ∼14–15%.  相似文献   

20.
A method is described to separate trace amounts of selenium in biological samples without using a carrier. This method is based on the adsorption on active carbon of the complex ion formed with APDC /ammonium salt of l-pyrrolidine carbodithioic acid/ at pH 1. The efficiency of the radiochemical separation described is measured by using carrier-free75Se labelled solutions of sodium selenite at selenium concentrations from 3.5×10–8 to 3.5×10–11 g ml–1. The results were between 95% and 98% with statistical variations from 2% to 10%. The determination of selenium can be made following this separation either through75Se in the traditional way, or through77mSe if the separation is performed prior to irradiation. The detection limits on the available conditions were 0.01 ppm for75Se and 0.1 ppm for77mSe. When the analysis is performed through75Se /t=120 d/, the statistical error is notably smaller because the counting time may be considerable, whereas through77mSe/t=17.5 s/it is higher than 20%, depending on the concentration and the available neutron flux. However, the advantages of gaining time and the fact of performing the trace separation from a non radioactive material, make both procedures competitive as useful tools for the research on the function of Se in vertebrates.  相似文献   

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