Arsenic removal by adsorption on iron(III) phosphate

Under natural conditions, arsenic is often associated with iron oxides and iron(III) oxidative capacity towards As(III) is well known. In this study, As(III) and As(V) removal was performed using synthesised iron(III) phosphate, either amorphous or crystalline. This solid can combine (i) As(III) oxidation by iron(III) and (ii) phosphate substitution by As(V) due to their similar properties. Results showed that adsorption capacities were higher towards As(III), leading to Fe2+ and HAsO4(2-) leaching. Solid dissolution and phosphate/arsenate exchange led to the presence of Fe3+ and PO4(3-) in solution, therefore various precipitates involving As(V) can be produced: with Fe2+ as Fe3(AsO4)2.8H2O(s) and with Fe3+ as FeAsO4.2H2O(s). Such formations have been assessed by thermodynamic calculations. This sorbent can be a potential candidate for industrial waste treatment, although the high release of phosphate and iron will exclude its application in drinking water plants.     

Removal of arsenic from water by zero-valent iron

Batch and column experiments were conducted to investigate the effect of dissolved oxygen (DO) and pH on arsenic removal with zero-valent iron [Fe(0)]. Arsenic removal was dramatically affected by the DO content and the pH of the solution. Under oxic conditions, arsenate [As(V)] removal by Fe(0) filings was faster than arsenite [As(III)]. Greater than 99.8% of the As(V) was removed whereas 82.6% of the As(III) was removed at pH 6 after 9h of mixing. When the solution was purged with nitrogen gas to remove DO, less than 10% of the As(III) and As(V) was removed. High DO content and low solution pH also increased the rate of iron corrosion. The removal of arsenic by Fe(0) was attributed to adsorption by iron hydroxides generated from the oxic corrosion of Fe(0). The column results indicated that a filtration system consisting of an iron column and a sand filter could be used for treatment of arsenic in drinking water.     

Elution and decomposition of cyanide in soil contaminated with various cyanocompounds

Standard soil samples contaminated with various standard cyanocompounds were prepared. Column elution experiments and analyses were conducted. Compounds with an easy capacity for dissociation to ions, such as KCN and potassium hexacyanoferrate(III), were found to be eluted by forming free cyanide even in fresh water. Hexacyanoferrate(II) salts, such as potassium hexacyanoferrate(II) and iron(III) hexacyanoferrate(II), were found not to be dissociated in water, but were dissociated and diffused under alkaline conditions (pH >13). Hexacyanoferrate(II) ion was found to be more easily dissociated in water with a higher pH.Column tests as above were also conducted for soil samples taken from a former paint ink factory using iron(III) hexacyanoferrate(II), cyanogen chloride, potassium cyanate, copper cyanide, as well as potassium cyanide, as raw materials. It was demonstrate that iron(III) hexacyanoferrate(II) was dissociated and eluted under alkaline conditions. The elution rate was reduced when the contaminated soil was sandwiched with standard soil layers.Further, it was found that the Fe(CN)(6)(4-) ion eluted with NaOH from hexacyanoferrate acid in soil, were easily decomposed into cyanic acid or other byproducts by UV with the addition of ozone and H(2)O(2).     

Removal of Fe(II) from tap water by electrocoagulation technique

Electrocoagulation (EC) is a promising electrochemical technique for water treatment. In this work electrocoagulation (with aluminum as electrodes) was studied for iron Fe(II) removal from aqueous medium. Different concentration of Fe(II) solution in tap water was considered for the experiment. During EC process, various amorphous aluminum hydroxides complexes with high sorption capacity were formed. The removal of Fe(II) was consisted of two principal steps; (a) oxidation of Fe(II) to Fe(III) and (b) subsequent removal of Fe(III) by the freshly formed aluminum hydroxides complexes by adsorption/surface complexation followed by precipitation. Experiments were carried out with different current densities ranging from 0.01 to 0.04 A/m². It was observed that the removal of Fe(II) increases with current densities. Inter electrode distance was varied from 0.005 to 0.02 m and was found that least inter electrode distance is suitable in order to achieve higher Fe(II) removal. Other parameters such as conductivity, pH and salt concentration were kept constant as per tap water quality. Satisfactory iron removal of around 99.2% was obtained at the end of 35 min of operation from the initial concentration of 25 mg/L Fe(II). Iron concentration in the solution was determined using Atomic absorption spectrophotometer. By products obtained from the electrocoagulation bath were analyzed by SEM image and corresponding elemental analysis (EDAX). Cost estimation for the electrocoagulation was adopted and explained well. Up to 15 mg/L of initial Fe(II) concentration, the optimum total cost was 6.05 US$/m³. The EC process for removing Fe(II) from tap water is expected to be adaptable for household use.     

Photo degradation of methyl orange an azo dye by advanced Fenton process using zero valent metallic iron: influence of various reaction parameters and its degradation mechanism

Advanced Fenton process (AFP) using zero valent metallic iron (ZVMI) is studied as a potential technique to degrade the azo dye in the aqueous medium. The influence of various reaction parameters like effect of iron dosage, concentration of H(2)O(2)/ammonium per sulfate (APS), initial dye concentration, effect of pH and the influence of radical scavenger are studied and optimum conditions are reported. The degradation rate decreased at higher iron dosages and also at higher oxidant concentrations due to the surface precipitation which deactivates the iron surface. The rate constant for the processes Fe(0)/UV and Fe(0)/APS/UV is twice compared to their respective Fe(0)/dark and Fe(0)/APS/dark processes. The rate constant for Fe(0)/H(2)O(2)/UV process is four times higher than Fe(0)/H(2)O(2)/dark process. The increase in the efficiency of Fe(0)/UV process is attributed to the cleavage of stable iron complexes which produces Fe(2+) ions that participates in cyclic Fenton mechanism for the generation of hydroxyl radicals. The increase in the efficiency of Fe(0)/APS/UV or H(2)O(2) compared to dark process is due to continuous generation of hydroxyl radicals and also due to the frequent photo reduction of Fe(3+) ions to Fe(2+) ions. Though H(2)O(2) is a better oxidant than APS in all respects, but it is more susceptible to deactivation by hydroxyl radical scavengers. The decrease in the rate constant in the presence of hydroxyl radical scavenger is more for H(2)O(2) than APS. Iron powder retains its recycling efficiency better in the presence of H(2)O(2) than APS. The decrease in the degradation rate in the presence of APS as an oxidant is due to the fact that generation of free radicals on iron surface is slower compared to H(2)O(2). Also, the excess acidity provided by APS retards the degradation rate as excess H(+) ions acts as hydroxyl radical scavenger. The degradation of Methyl Orange (MO) using Fe(0) is an acid driven process shows higher efficiency at pH 3. The efficiency of various processes for the de colorization of MO dye is of the following order: Fe(0)/H(2)O(2)/UV>Fe(0)/H(2)O(2)/dark>Fe(0)/APS/UV>Fe(0)/UV>Fe(0)/APS/dark>H(2)O(2)/UV approximately Fe(0)/dark>APS/UV. Dye resisted to degradation in the presence of oxidizing agent in dark. The degradation process was followed by UV-vis and GC-MS spectroscopic techniques. Based on the intermediates obtained probable degradation mechanism has been proposed. The result suggests that complete degradation of the dye was achieved in the presence of oxidizing agent when the system was amended with iron powder under UV light illumination. The concentration of Fe(2+) ions leached at the end of the optimized degradation experiment is found to be 2.78 x 10(-3)M. With optimization, the degradation using Fe(0) can be effective way to treat azo dyes in aqueous solution.     

Arsenic (III,V) removal from aqueous solution by ultrafine α-Fe2O3 nanoparticles synthesized from solvent thermal method

Ultrafine iron oxide (α-Fe₂O₃) nanoparticles were synthesized by a solvent thermal process and used to remove arsenic ions from both lab-prepared and natural water samples. The α-Fe₂O₃ nanoparticles assumed a near-sphere shape with an average size of about 5 nm. They aggregated into a highly porous structure with a high specific surface area of ∼162 m²/g, while their surface was covered by high-affinity hydroxyl groups. The arsenic adsorption experiment results demonstrated that they were effective, especially at low equilibrium arsenic concentrations, in removing both As(III) and As(V) from lab-prepared and natural water samples. Near the neutral pH, the adsorption capacities of the α-Fe₂O₃ nanoparticles on As(III) and As(V) from lab-prepared samples were found to be no less than 95 mg/g and 47 mg/g, respectively. In the presence of most competing ions, these α-Fe₂O₃ nanoparticles maintained their arsenic adsorption capacity even at very high competing anion concentrations. Without the pre-oxidation and/or the pH adjustment, these α-Fe₂O₃ nanoparticles effectively removed both As(III) and As(V) from a contaminated natural lake water sample to meet the USEPA drinking water standard for arsenic.     

A laboratory study for the treatment of arsenic, iron, and manganese bearing ground water using Fe(3+) impregnated activated carbon: effects of shaking time, pH and temperature

This paper deals with the experimental investigation related to removal of arsenic from a simulated contaminated ground water by the adsorption onto Fe(3+) impregnated granular activated carbon (GAC-Fe) in presence of Fe(2+), Fe(3+), and Mn(2+). Similar study has also been done with granular activated carbon (GAC) for comparison. The effects of shaking time, pH, and temperature on the percentage removal of As(T), As(III), As(V), Fe(2+), Fe(3+), and Mn have been discussed. The shaking time for optimum removal of arsenic species has been noted as 8h for GAC-Fe and 12h for GAC, respectively. As(T) removal was less affected by the change in pH within the pH range of 2-11. Maximum removal of As(V) and As(III) was observed in the pH range of 5-7 and 9-11, respectively, for both the adsorbents. Under the experimental conditions at 30 degrees C, the optimum removal of As(T), As(III), As(V), Fe, and Mn are 95.5%, 93%, 98%, 100%, and 41%, respectively, when GAC-Fe is used. For GAC these values are 56%, 41%, 71%, 99%, and 98%. The adsorbent dose (AD) and its particle size (PS) for both GAC and GAC-Fe were 30 g/l and 125-150 mum, respectively. The initial arsenic concentration in the synthetic water sample was 200 ppb.     

Oxidation of arsenic bearing fly ash as pretreatment before solidification.

When a waste fly ash, containing large amounts of As(2)O(3), is solidified using cement and lime, the arsenic concentration in the leachate (extraction test DIN 38 414 S4) is determined by the solubility of CaHAsO(3) and can be lowered to a value of ca. 5 mg/l, in a saturated solution of Ca(OH)(2). One of the criteria for landfilling of hazardous waste is, however, that the arsenic concentration in the leachate must be lower than 1 mg/l. In this paper, it is shown that oxidation of the waste before solidification, whereby As(III) is oxidised to As(V) using H(2)O(2), lowers the leaching of arsenic, and other contaminants, from the solidified product. With the speciation program MINTEQA2, it is calculated that the solubility of As(V) in the presence of a pure Ca(3)(AsO(4))(2) precipitate is lower than the solubility of As(III) in the presence of a pure CaHAsO(3) precipitate. The arsenic concentration in the presence of both a Ca(OH)(2) and a Ca(3)(AsO(4))(2) precipitate can even be lowered to 0.47 mg/l (pH 12.5). The As concentration in the leachate of the extraction test on an oxidised S/S sample was indeed lowered to ca. 0.5 mg/l, which is a reduction by a factor of 10 compared to the concentration of ca. 5 mg/l, obtained in the leachate of the extraction test on a non-oxidised S/S sample. This is in very good agreement with the calculated value of 0.47 mg/l. Also, the pretreatment decreased the cumulative fraction of arsenic released over the entire test period of a semi-dynamic leach test by a factor of 7. At all times during the test, the As concentration did not exceed the norm of 1 mg/l.     

Effect of Mn substitution on the oxidation/adsorption abilities of iron(III) oxyhydroxides

In this study, divalent manganese ions [Mn(II)] were substituted a part of divalent iron ions [Fe(II)] present in Fe oxyhydroxides to prepare novel composites (Mn@Feox). The composites were prepared by (1) simultaneous hydrolysis of Fe(II) and Mn(II), and (2) rapid oxidation with H₂O₂. The resulting Mn@Feox prepared with different molar ratios of Fe and Mn was characterized and evaluated for their abilities to adsorb arsenic species [As(III) and As(V)] in aqueous solution. X-ray diffraction and field emission transmission electron microscope analyses revealed Mn@Feox has a δ-(Fe_1?x, Mn_x)OOH-like structure with their mineralogical properties resembling those of feroxyhyte (δ-FeOOH). The increase in Mn substitution in Mn@Feox enhanced the oxidative ability to oxidize As(III) to As(V), but it decreased the adsorption capacity for both arsenic species. The optimal Mn/Fe molar ratio that could endow oxidation and magnetic capabilities to the composite without significantly compromising As adsorption capability was determined to be 0.1 (0.1Mn@Feox). The adsorption of As(III) on 0.1Mn@Feox was weakly influenced by pH change while As(V) adsorption showed high dependence on pH, achieving nearly complete removal at pH?<?5.7 but gradual decrease at pH?>?5.7. The adsorption kinetics and isotherms of As(III) and As(V) showed good conformity to pseudo-second-order kinetics model and Freundlich model, respectively.     

Characterization of arsenic (V) and arsenic (III) in water samples using ammonium molybdate and estimation by graphite furnace atomic absorption spectroscopy

Arsenic (V) is known to form heteropolyacid with ammonium molybdate in acidic aqueous solutions, which can be quantitatively extracted into certain organic solvents. In the present work, 12-molybdoarsenic acid extracted in butan-1-ol is used for quantification of As (V). Total arsenic is estimated by converting arsenic (III) to arsenic (V) by digesting samples with concentrated nitric acid before extraction. Concentration of As (III) in the sample solutions could be calculated by the difference in total arsenic and arsenic (V). The characterization of arsenic was carried out by GFAAS using Pd as modifier. Optimization of the experimental conditions and instrumental parameters was investigated in detail. Recoveries of (90-110%) were obtained in the spiked samples. The detection limit was 0.2 microg l(-1). The proposed method was successfully applied for the determination of trace amount of arsenic (III) and arsenic (V) in process water samples.     

Assessing arsenic leachability from pulverized cement concrete produced from arsenic-laden solid CalSiCo-sludge

Synthetically prepared arsenic-laden CalSiCo-sludge was converted to pulverized cement concrete (PCC) using solidification/stabilization technology with cement. Batch leaching experiments were conducted to estimate the leaching of As(III) and As(V) from the CalSiCo-sludge as well as from the PCC. The leaching of As(III) and As(V) was found to be the function of time, pH and concentration of anions such as Cl(-), NO(3)(-), and SO(4)(2-) present in the extraction fluid. It is observed that from the CalSiCo-sludge the leaching of As(III) is >0.05mg/l (which is above the permissible limit for arsenic in drinking water) at any pH. But in case of As(V) the leaching is >0.05mg/l only at pH>8 and at pH<4. It is noted that maximum leaching occurs when the extraction liquid contains Cl(-). In contrary, NO(3)(-) and SO(4)(2-) have negligible effect on arsenic leaching from the CalSiCo-sludge. Extraction tests were carried out to determine the maximum leachable concentration under the chosen conditions of leaching medium and leaching time. Leaching of As(III) and As(V) from exhausted arsenic-laden CalSiCo-sludge and from PCC was carried out in both tap water and rain water. It was noticed that tap water has no effect in leaching of arsenic from CalSiCo-sludge but rain water causes significant amount of leaching, which is mostly due to pH effect. However, in all cases the leaching of As(III) was more than that of As(V). When compared with CalSiCo-sludge PCC showed negligible leaching of arsenic. It was noticed further that the variation of 28 days compressive strength was within 15% of the original strength after replacing 35% cement with exhausted CalSiCo-sludge.     

Speciation of dissolved iron(III) and iron(II) in water by on-line coupling of flow injection separation and preconcentration with inductively coupled plasma mass spectrometry

A method has been developed for the speciation of trace dissolved Fe(II) and Fe(II) in water by on-line coupling of flow injection separation and preconcentration with inductively coupled plasma mass spectrometry (ICPMS). Selective determination of Fe(III) in the presence of Fe(II) was made possible by on-line formation and sorption of the Fe(III)-pyrrolidinecarbodithioate (PDC) complex in a PTFE knotted reactor over a sample acidity range of 0.07-0.4 mol L(-1) HCl, elution with 1 mol L(-1) HNO3, and detection by ICPMS. Over a sample acidity range of 0.001-0.004 mol L(-1) HCl, the sum of Fe(III) and Fe(II), i.e., Fe(III + II), could be determined without the need for preoxidation of Fe(II) to Fe(III). The concentration of Fe(II) was obtained as the difference between those of Fe(III + II) and Fe(III). With a sample flow rate of 5 mL min(-1) and a 30-s preconcentration time, an enhancement factor of 12, a retention efficiency of 80%, and a detection limit (3s) of 0.08 microg L(-1) were obtained at a sampling frequency of 21 samples h(-1). The relative standard deviation (n = 11) was 2.9% at the 10 microg L(-1) Fe(III) level. Recoveries of spiked Fe(III) and Fe(II) in local tap water, river water, and groundwater samples ranged from 95% to 103%. The concentrations of Fe(III) and Fe(II) in synthetic aqueous mixtures obtained by the proposed method were in good agreement with the spiked values. The result for total iron concentration in the river water reference material SLRS-3 was in good agreement with the certified value. The method was successfully applied to the determination of trace dissolved Fe(III) and Fe(II) in local tap water, river water, and groundwater samples.     

Diaion SP-850 resin as a new solid phase extractor for preconcentration-separation of trace metal ions in environmental samples

A solid phase extraction method was developed for the preconcentration and separation of trace amounts of chromium, manganese, iron, cobalt, copper, cadmium and lead from environmental samples by complexation with alpha-benzoin oxime followed by adsorption onto Diaion SP-850-solid phase extraction column. One molar per liter HNO(3) was used as eluent. The recoveries of analytes at pH 8.0 with 700 mg of resin were greater than 95% without interference from alkaline, earth alkaline and some metal ions. The detection limits by three sigma for analyte ions were 0.65 microg l(-1) for Cr(III), 0.42 microg l(-1) for Mn(II), 0.28 microg l(-1) for Fe(III), 0.73 microg l(-1) for Co(II), 0.30 microg l(-1) for Cu(II), 0.47 microg l(-1) for Cd(II) and 0.50 microg l(-1) for Pb(II). The validation of the procedure was performed by the analysis of the certified standard reference materials. The presented procedure was applied to the determination of analytes in tap, river and sea waters, rice, wheat, canned tomato and coal samples with successfully results (recoveries greater than 95%, R.S.D.'s lower than 8%).     

Reduction of chromate from electroplating wastewater from pH 1 to 2 using fluidized zero valent iron process

Fluidized zero valent iron (ZVI) process was conducted to reduce hexavalent chromium (chromate, CrO(4)(2-)) to trivalent chromium (Cr(3+)) from electroplating wastewater due to the following reasons: (1) Extremely low pH (1-2) for the electroplating wastewater favoring the ZVI reaction. (2) The ferric ion, produced from the reaction of Cr(VI) and ZVI, can act as a coagulant to assist the precipitation of Cr(OH)(3(s)) to save the coagulant cost. (3) Higher ZVI utilization for fluidized process due to abrasive motion of the ZVI. For influent chromate concentration of 418 mg/L as Cr(6+), pH 2 and ZVI dosage of 3g (41 g/L), chromate removal was only 29% with hydraulic detention time (HRT) of 1.2 min, but was increased to 99.9% by either increasing HRT to 5.6 min or adjusting pH to 1.5. For iron species at pH 2 and HRT of 1.2 min, Fe(3+) was more thermodynamically stable since oxidizing agent chromate was present. However, if pH was adjusted to 1.5 or 1, where chromate was completely removed, high Fe(2+) but very low Fe(3+) was present. It can be explained that ZVI reacted with chromate to produce Fe(2+) first and the presence of chromate would keep converting Fe(2+) to Fe(3+). Therefore, Fe(2+) is an indicator for complete reduction from Cr(VI) to Cr(III). X-ray diffraction (XRD) was conducted to exam the remained species at pH 2. ZVI, iron oxide and iron sulfide were observed, indicating the formation of iron oxide or iron sulfide could stop the chromate reduction reaction.     

Effects of adsorbent dose, its particle size and initial arsenic concentration on the removal of arsenic, iron and manganese from simulated ground water by Fe3+ impregnated activated carbon

This paper presents the observations of the study on arsenic removal from a contaminated ground water (simulated) by adsorption onto Fe³⁺ impregnated granular activated carbon (GAC-Fe). Fe²⁺, Fe³⁺ and Mn²⁺ have also been considered along with arsenic species in the water sample. Similar study has also been done with untreated granular activated carbon (GAC) for comparison. The effects of adsorbent dose, particle size of adsorbent and initial arsenic concentration on the removal of As(T), As(III), As(V), Fe²⁺, Fe³⁺ and Mn²⁺ have been discussed. Under the experimental conditions, the optimum adsorbent doses for GAC-Fe and GAC have been found to be 8 g/l and 24 g/l, respectively with an agitation time of 15 h. Particle size of the adsorbents (both GAC and GAC-Fe) has shown negligible effect on the removal of arsenic and Fe species. However, for Mn removal the effect of adsorbent particle size is comparatively more. Percentage removal of As(T), As(V) and As(III) increase with the decrease in initial arsenic concentration (As₀). However, the increase in percentage removal of all the arsenic species with decrease in As₀ are less for higher value of As₀ (3000–500 ppb) than those of the lower value of As₀ (500–10 ppb). The % removal of As(T), As(III), As(V), Fe, and Mn were 95%, 92.4%, 97.6%, 99% and 41.2%, respectively when 8 g/l GAC-Fe was used at the As₀ value of 200 ppb. However, for GAC these values were 55.5%, 44%, 71%, 98% and 97%. The pH and temperature of the study were 7 ± 0.1 and 30 ± 1 °C, respectively.     

Arsenate removal by zero valent iron: Batch and column tests

This study investigates the efficiency of zero valent iron (ZVI) to remove arsenate from water. Batch experiments were carried out to study the removal kinetics of arsenate under different pH values and in the presence of low and high concentrations of various anions (chloride, carbonate, nitrate, phosphate, sulphate and borate), manganese and dissolved organic matter. Borate and organic matter, particularly at higher concentrations, inhibited the removal of arsenic. Column tests were carried out to investigate the removal of arsenate from tap water under dynamic conditions. The concentrations of arsenic and iron as well as the pH and Eh were measured in treated water. Efficient removal of arsenate was observed resulting at concentrations below the limit of 10 μg/L in treated waters.     

Luminol chemiluminescence in unbuffered solutions with a cobalt(II)-ethanolamine complex immobilized on resin as catalyst and its application to analysis.

Using a heterogeneous catalyst, Co(II)-ethanolamine complex sorbed on Dowex-50W resin, the chemiluminescence (CL) of luminol in unbuffered or weakly acidic solution was studied in the presence of H2O2. The maximum luminol CL wavelength at pH 5.7 was 448 nm, 23 nm longer than that in a basic solution (pH 10.5). Three different ligands, mono-, di-, and triethanolamine, and six transition metal ions, Co(II), Cu(II), Ni(II), Mn-(II), Fe(II), and Fe(III) were compared by CL measurements. The CL intensity decreased in the order mono- > di- > triethanolamine and Co(II) > Cu(II) > Ni(II) > Fe-(III) > Mn(II) > Fe(II). This heterogeneous CL system was developed as H2O2 and glucose flow-through sensors. Detection limits (S/N = 3) of H2O2 and glucose using Dowex-50W-X4-Co(II)-monoethanolamine as catalyst are 1 x 10(-7) M and 1 x 10(-6) M, respectively. On the basis of the studies of the CL, fluorescence, UV-vis and ESCA spectra and the effect of dissolved oxygen in luminol solution, a mechanism for CL emission in unbuffered solution was considered as the formation of a superoxide radical ion during the decomposition of H2O2 catalyzed by the Co(II)-ethanolamine immobilized resin. Then the superoxide radical ion acted on luminol and the CL was emitted. The applications of the proposed method to determine H2O2 in rainwater without any special pretreatment and glucose in human urine and orange juice samples give satisfactory results.     

Determination of the elemental composition of molasses and its suitability as carbon source for growth of sulphate-reducing bacteria

Bioremediation of arsenic-contaminated water could be a cost-effective process provided a cheap carbon source is used. In this work molasses was tested as a possible source of carbon for the growth of sulphate-reducing bacteria (SRB). Its elemental composition and the tolerance of SRB toward different arsenic species (As (III) and As (V)) were also investigated. Batch studies were carried out to assess the suitability of 1, 2.5 and 5 g/l molasses concentrations for SRB growth. The results indicated that molasses does support SRB growth, the level of response being dependant on the concentration. The percentage of sulphate reduction with molasses at 1, 2.5 and 5 g/l was not significantly different. However, growth on molasses was not as good as that obtained when lactate was used as carbon source. Molasses contained the heavy metals Al, As, Cu, Fe, Mn and Zn in concentrations of 0.54, 0.24, 8.7, 0.35, 11.1 and 19.7 microg/g, respectively. Arsenic tolerance, growth response and sulphate-reducing activity of the SRB were investigated using arsenite and arsenate solutions at final concentrations of 1, 5 and 20 mg/l for each species. The results revealed that very little SRB growth occurred at concentrations of 20 mg/l As(III) or As(V). At lower concentrations (1 mg/l) the SRB grew better with As(V) than with As(III). Arsenic pollution in most groundwater sources is below this level (1 mg/l).     

Design of a neutral electro-Fenton system with Fe@Fe(2)O(3)/ACF composite cathode for wastewater treatment

The narrow pH range limits the wide application of Fenton reaction in the wastewater treatment. It is of great importance to widen working pH range of Fenton reaction from strong acidic condition to neutral, even basic ones. In this study, for the first time nanostructured Fe@Fe(2)O(3) was loaded on active carbon fiber (ACF) as an oxygen diffusion cathode to be used in a heterogeneous electro-Fenton (E-Fenton) oxidation system. This novel Fe@Fe(2)O(3)/ACF composite cathode was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analysis, transmission electron microscopy (TEM), and element mapping. On the degradation of dye pollutant rhodamine B in water, this heterogeneous E-Fenton system with the Fe@Fe(2)O(3)/ACF cathode showed much higher activity than other E-Fenton systems with commercial zero valent iron powders (Fe(0)) and ferrous ions (Fe(2+)) under neutral pH. On the basis of experimental results, we proposed a possible pathway of rhodamine B degradation in this heterogeneous Fe@Fe(2)O(3)/ACF E-Fenton process. This heterogeneous E-Fenton system is very promising to remove organic pollutants in water at neutral pH.     

Flow injection on-line sorption preconcentration coupled with hydride generation atomic fluorescence spectrometry for determination of (ultra)trace amounts of arsenic(III) and arsenic(V) in natural water samples

A flow injection on-line sorption preconcentration and separation in a knotted reactor (KR) was coupled to hydride generation atomic fluorescence spectrometry (HG-AFS) for speciation of inorganic arsenic in natural water samples. The method involved on-line formation of the As(III)-pyrrolidinedithiocarbamate (PDC) complex over a sample acidity of 0.001-0.1 mol L(-1) HCl, its adsorption onto the inner walls of the KR made from 150-cm long x 0.5-mm i.d. PTFE tubing, elution withmol L(-1) HCl, and detection by HG-AFS. Total inorganic arsenic was determined after prereduction of As(V) to As(III) with 1% m/v L-cysteine. The concentration of As(V) was calculated by the difference of the total inorganic arsenic and As(III). A 1 mol L(-1) concentration of HCl was employed not only as the efficient eluent but also as the required medium for subsequent hydride generation. Potential factors that affect adsorption, rinsing, elution, and hydride generation were investigated in detail. The low cost, easy operation, and high sensitivity are the obvious advantages of the present system. With consumption of a 6 mL sample solution, an enhancement factor of 11 and a detection limit (3s) of 0.023 microg L(-1) As(III) were obtained at a sample throughput of 32 h(-1). The precision for 14 replicate measurements of 1 microg L(-1) As(III) was 1.3% (RSD). The recoveries from natural water samples varied from 96.7 to 105% for 2 microg L(-1) of As(III) spike and from 97.1 to 107% for 2 microg L(-1) of As(V) spike. The analytical results obtained by the present method for total arsenic in the certified reference materials, SLRS-4 (river water) and NASS-5 (seawater), agreed well with the certified values. The developed method was also successfully applied to the speciation of inorganic arsenic in local natural water samples.